Science.gov

Sample records for aerosol mass fractions

  1. Mass balance of organic carbon fractions in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Alves, CéLia; Carvalho, Abel; Pio, Casimiro

    2002-11-01

    Total suspended particulate matter was collected in two Portuguese urban areas (Lisbon and Aveiro) and in a Finnish forested site. Samples were sequentially extracted with dichloromethane and water. The solvent extract was separated by flash chromatography into aliphatics, aromatics, carbonyls, alcohols, and an acidic fraction, and analyzed by gas chromatography-mass spectrometry. An organic/black carbon analyzer was used to evaluate the carbonaceous matter in filters, the water-soluble fraction, solvent extractable material, and the content of different organic classes. Results showed that the common simple extraction with dichloromethane is able to dissolve less than 50% of the particulate organic material. The successive extraction with water removes an important quantity of the leftover organic polar compounds. The sum of both extractions recovers between 70% and 90% of the organic carbon present. The amount of oxygenated compounds is frequently more than 70% of the extracted material, with a large predominance of organic acids and alcohols, especially for particles with diameters less than 0.49 μm. The organic compounds identified in the extractable atmospheric particulate matter are represented by primary compounds with both anthropogenic and biogenic origin, which mainly derive from vegetation waxes and from petrogenic sources. Secondary products resulting from the oxidation of volatile organic compounds were also detected. The water-soluble fraction contains essentially oxocarboxylic and dicarboxylic acids, and cellulosic constituents. In accordance with the anthropogenic characteristics of the sampling sites, nonpolar fractions constitute up to 24% of the extracted organic carbon in Lisbon and present high levels of petroleum markers, while in the forested station these compounds represent 8%. The oxygenated organic compounds account for 76-92% of the extracted carbon in samples from Aveiro and Finland. Owing to favorable photochemical conditions during

  2. Ozonolysis of beta-pinene: temperature dependence of secondary organic aerosol mass fraction.

    PubMed

    Pathak, Ravikant; Donahue, Neil M; Pandis, Spyros N

    2008-07-15

    The SOA formation from beta-pinene ozonolysis at modest precursor concentrations (2-40 ppb) was investigated in the temperature range of 0-40 degrees C. The presence of inert seeds and high ozone concentrations is necessary to minimize losses of semivolatile vapors to the walls of the smog chamber. beta-pinene secondary organic aerosol production increases significantly with decreasing temperature. An increase by a factor of 2-3, depending on the reacted beta-pinene concentration, was observed as the temperature decreased from 40 to 0 degrees C. This increase appearsto be due mainly to the shifting of partitioning of the semivolatile SOA componentstoward the particulate phase and not to a change of the beta-pinene product distribution with temperature. The measurements are used to develop a new temperature-dependent parametrization for the four-component basis-set. The parametrization predicts much higher SOA production for beta-pinene ozonolysis for typical atmospheric conditions than the values that have been suggested by previous studies.

  3. Oxygenated fraction and mass of organic aerosol from direct emission and atmospheric processing measured on the R/V Ronald Brown during TEXAQS/GoMACCS 2006

    NASA Astrophysics Data System (ADS)

    Russell, L. M.; Takahama, S.; Liu, S.; Hawkins, L. N.; Covert, D. S.; Quinn, P. K.; Bates, T. S.

    2009-04-01

    Submicron particles collected on Teflon filters aboard the R/V Ronald Brown during the Texas Air Quality Study and Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS/GoMACCS) 2006 in and around the port of Houston, Texas, were measured by Fourier transform infrared (FTIR) and X-ray fluorescence for organic functional groups and elemental composition. Organic mass (OM) concentrations (1-25 μg m-3) for ambient particle samples measured by FTIR showed good agreement with measurements made with an aerosol mass spectrometer. The fractions of organic mass identified as alkane and carboxylic acid groups were 47% and 32%, respectively. Three different types of air masses were identified on the basis of the air mass origin and the radon concentration, with significantly higher carboxylic acid group mass fractions in air masses from the north (35%) than the south (29%) or Gulf of Mexico (26%). Positive matrix factorization analysis attributed carboxylic acid fractions of 30-35% to factors with mild or strong correlations (r > 0.5) to elemental signatures of oil combustion and 9-24% to wood smoke, indicating that part of the carboxylic acid fraction of OM was formed by the same sources that controlled the metal emissions, namely the oil and wood combustion activities. The implication is that a substantial part of the measured carboxylic acid contribution was formed independently of traditionally "secondary" processes, which would be affected by atmospheric (both photochemical and meteorological) conditions and other emission sources. The carboxylic acid group fractions in the Gulf of Mexico and south air masses (GAM and SAM, respectively) were largely oil combustion emissions from ships as well as background marine sources, with only limited recent land influences (based on radon concentrations). Alcohol groups accounted for 14% of OM (mostly associated with oil combustion emissions and background sources), and amine groups accounted for 4% of OM in all air

  4. Nitrogen fractionation in Titan's aerosols

    NASA Astrophysics Data System (ADS)

    Carrasco, Nathalie; Kuga, Maia; Marty, Bernard; Fleury, Benjamin; Marrocchi, Yves

    2016-06-01

    A strong nitrogen fractionation is found by Cassini in Titan's atmosphere with the detection of 15N-rich HCN relative to N2. Photodissociation of N2 associated or not to self-shielding might involve 15N-rich radicals prone to incorporation into forming organics. However the isotopic composition is only available for very simple gaseous N-bearing compounds, and the propagation and conservation of such a large N-isotopic fractionation upon polymerization is actually out of reach with the instruments onboard Cassini. We will therefore present a first laboratory investigation of the possible enrichment in the solid organic aerosols. We will also discuss the space instrumention required in the future to answer this pending issue on Titan.

  5. Chemical Structural Characteristics of HULIS and Other Fractionated Organic Matter in Urban Aerosols: Results from Mass Spectral and FT-IR Analysis.

    PubMed

    Chen, Qingcai; Ikemori, Fumikazu; Higo, Hayato; Asakawa, Daichi; Mochida, Michihiro

    2016-02-16

    The chemical characteristics of complex organic matter in atmospheric aerosols remain poorly understood. Water-insoluble organic matter (WISOM) and water-soluble organic matter (WSOM) in the total suspended particulates collected in the city of Nagoya in summer/early autumn and winter were extracted using multiple solvents. Two fractions of humic-like substances, showing neutral and acidic behavior (HULIS-n and HULIS-a, respectively), and the remaining highly polar part (HP-WSOM) were fractionated from WSOM using solid phase extraction. The chemical structural characteristics and concentrations of the organic matter were investigated using mass spectrometry and Fourier transform infrared (FT-IR) spectroscopy. WISOM and HULIS-n had low O/C ratios (0.1 and 0.4, respectively) and accounted for a large fraction of the organics in aerosols (70%). HULIS-a and HP-WSOM had higher O/C ratios (0.7 and 1.0, respectively), and their concentrations in summer and early autumn were on average ∼2 times higher than those in winter. The mass spectrum and FT-IR analyses suggest the following: (1) WISOM were high-molecular-weight aliphatics (primarily C27-C32) with small proportions of -CH3, -OH, and C═O groups; (2) HULIS-n was abundant in aliphatic structures and hydroxyl groups (primarily C9-C18) and by branched structures; (3) HULIS-a and HP-WSOM contained relatively large amounts of low-molecular-weight carboxylic acids and alcohols (primarily C4-C10); and (4) WISOM and HULIS-n were relatively abundant in amines and organic nitrates. PMID:26771766

  6. Analysis of the unresolved organic fraction in atmospheric aerosols with ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy: organosulfates as photochemical smog constituents.

    PubMed

    Schmitt-Kopplin, Philippe; Gelencsér, Andras; Dabek-Zlotorzynska, Ewa; Kiss, Gyula; Hertkorn, Norbert; Harir, Mourad; Hong, Yang; Gebefügi, Istvan

    2010-10-01

    Complementary molecular and atomic signatures obtained from Fourier transform ion cyclotron resonance (FTICR) mass spectra and NMR spectra provided unequivocal attribution of CHO, CHNO, CHOS, and CHNOS molecular series in secondary organic aerosols (SOA) and high-resolution definition of carbon chemical environments. Sulfate esters were confirmed as major players in SOA formation and as major constituents of its water-soluble fraction (WSOC). Elevated concentrations of SO(2), sulfate, and photochemical activity were shown to increase the proportion of SOA sulfur-containing compounds. Sulfonation of CHO precursors by means of heterogeneous reactions between carbonyl derivatives and sulfuric acid in gas-phase photoreactions was proposed as a likely formation mechanism of CHOS molecules. In addition, photochemistry induced oligomerization processes of CHOS molecules. Methylesters found in methanolic extracts of a SOA subjected to strong photochemical exposure were considered secondary products derived from sulfate esters by methanolysis. The relative abundance of nitrogen-containing compounds (CHNO and CHNOS series) appeared rather dependent on local effects such as biomass burning. Extensive aliphatic branching and disruption of extended NMR spin-systems by carbonyl derivatives and other heteroatoms were the most significant structural motifs in SOA. The presence of heteroatoms in elevated oxidation states suggests a clearly different SOA formation trajectory in comparison with established terrestrial and aqueous natural organic matter. PMID:20879800

  7. Analysis of the unresolved organic fraction in atmospheric aerosols with ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy: organosulfates as photochemical smog constituents.

    PubMed

    Schmitt-Kopplin, Philippe; Gelencsér, Andras; Dabek-Zlotorzynska, Ewa; Kiss, Gyula; Hertkorn, Norbert; Harir, Mourad; Hong, Yang; Gebefügi, Istvan

    2010-10-01

    Complementary molecular and atomic signatures obtained from Fourier transform ion cyclotron resonance (FTICR) mass spectra and NMR spectra provided unequivocal attribution of CHO, CHNO, CHOS, and CHNOS molecular series in secondary organic aerosols (SOA) and high-resolution definition of carbon chemical environments. Sulfate esters were confirmed as major players in SOA formation and as major constituents of its water-soluble fraction (WSOC). Elevated concentrations of SO(2), sulfate, and photochemical activity were shown to increase the proportion of SOA sulfur-containing compounds. Sulfonation of CHO precursors by means of heterogeneous reactions between carbonyl derivatives and sulfuric acid in gas-phase photoreactions was proposed as a likely formation mechanism of CHOS molecules. In addition, photochemistry induced oligomerization processes of CHOS molecules. Methylesters found in methanolic extracts of a SOA subjected to strong photochemical exposure were considered secondary products derived from sulfate esters by methanolysis. The relative abundance of nitrogen-containing compounds (CHNO and CHNOS series) appeared rather dependent on local effects such as biomass burning. Extensive aliphatic branching and disruption of extended NMR spin-systems by carbonyl derivatives and other heteroatoms were the most significant structural motifs in SOA. The presence of heteroatoms in elevated oxidation states suggests a clearly different SOA formation trajectory in comparison with established terrestrial and aqueous natural organic matter.

  8. Mexico city aerosol analysis during MILAGRO using high resolution aerosol mass spectrometry at the urban supersite (T0) - Part 2: Analysis of the biomass burning contribution and the non-fossil carbon fraction

    SciTech Connect

    Aiken, A.C.; Wang, J.; de Foy, B.; Wiedinmyer, C.; DeCarlo, P. F.; Ulbrich, I. M.; Wehrli, M. N.; Szidat, S.; Prevot, A. S. H.; Noda, J.; Wacker, L.; Volkamer, R.; Fortner, E.; Laskin, A.; Shutthanandan, V.; Zheng, J.; Zhang, R.; Paredes-Miranda, G.; Arnott, W. P.; Molina, L. T.; Sosa, G.; Querol, X.; Jimenez, J. L.

    2010-06-16

    periods or a correlation with fire counts, FLEXPART-predicted FIFs or fire tracers, indicating that it is dominated by urban and/or regional sources and not by the fires near the MCMA. A new 14C aerosol dataset is presented. Both this new and a previously published dataset of 14C analysis suggest a similar BBOA contribution as the AMS and chemical mass balance (CMB), resulting in 13% higher non-fossil carbon during the high vs. low regional fire periods. The new dataset has {approx}15% more fossil carbon on average than the previously published one, and possible reasons for this discrepancy are discussed. During the low regional fire period, 38% of organic carbon (OC) and 28% total carbon (TC) are from non-fossil sources, suggesting the importance of urban and regional non-fossil carbon sources other than the fires, such as food cooking and regional biogenic SOA. The ambient BBOA/CH3CN ratio is much higher in the afternoon when the wildfires are most intense than during the rest of the day. Also, there are large differences in the contributions of the different OA components to the surface concentrations vs. the integrated column amounts. Both facts may explain some apparent disagreements between BB impacts estimated from afternoon aircraft flights vs. those from 24-h ground measurements. We show that by properly accounting for the non-BB sources of K, all of the BB PM estimates from MILAGRO can be reconciled. Overall, the fires from the region near the MCMA are estimated to contribute 15-23% of the OA and 7-9% of the fine PM at T0 during MILAGRO, and 2-3% of the fine PM as an annual average. The 2006 MCMA emissions inventory contains a substantially lower impact of the forest fire emissions, although a fraction of these emissions occur just outside of the MCMA inventory area.

  9. Mexico city aerosol analysis during MILAGRO using high resolution aerosol mass spectrometry at the urban supersite (T0) - Part 2: Analysis of the biomass burning contribution and the non-fossil carbon fraction

    NASA Astrophysics Data System (ADS)

    Aiken, A. C.; de Foy, B.; Wiedinmyer, C.; Decarlo, P. F.; Ulbrich, I. M.; Wehrli, M. N.; Szidat, S.; Prevot, A. S. H.; Noda, J.; Wacker, L.; Volkamer, R.; Fortner, E.; Wang, J.; Laskin, A.; Shutthanandan, V.; Zheng, J.; Zhang, R.; Paredes-Miranda, G.; Arnott, W. P.; Molina, L. T.; Sosa, G.; Querol, X.; Jimenez, J. L.

    2010-06-01

    correlation with fire counts, FLEXPART-predicted FIFs or fire tracers, indicating that it is dominated by urban and/or regional sources and not by the fires near the MCMA. A new 14C aerosol dataset is presented. Both this new and a previously published dataset of 14C analysis suggest a similar BBOA contribution as the AMS and chemical mass balance (CMB), resulting in 13% higher non-fossil carbon during the high vs. low regional fire periods. The new dataset has ~15% more fossil carbon on average than the previously published one, and possible reasons for this discrepancy are discussed. During the low regional fire period, 38% of organic carbon (OC) and 28% total carbon (TC) are from non-fossil sources, suggesting the importance of urban and regional non-fossil carbon sources other than the fires, such as food cooking and regional biogenic SOA. The ambient BBOA/ΔCH3CN ratio is much higher in the afternoon when the wildfires are most intense than during the rest of the day. Also, there are large differences in the contributions of the different OA components to the surface concentrations vs. the integrated column amounts. Both facts may explain some apparent disagreements between BB impacts estimated from afternoon aircraft flights vs. those from 24-h ground measurements. We show that by properly accounting for the non-BB sources of K, all of the BB PM estimates from MILAGRO can be reconciled. Overall, the fires from the region near the MCMA are estimated to contribute 15-23% of the OA and 7-9% of the fine PM at T0 during MILAGRO, and 2-3% of the fine PM as an annual average. The 2006 MCMA emissions inventory contains a substantially lower impact of the forest fire emissions, although a fraction of these emissions occur just outside of the MCMA inventory area.

  10. Workplace aerosol mass concentration measurement using optical particle counters.

    PubMed

    Görner, Peter; Simon, Xavier; Bémer, Denis; Lidén, Göran

    2012-02-01

    Direct-reading aerosol measurement usually uses the optical properties of airborne particles to detect and measure particle concentration. In the case of occupational hygiene, mass concentration measurement is often required. Two aerosol monitoring methods are based on the principle of light scattering: optical particle counting (OPC) and photometry. The former analyses the light scattered by a single particle, the latter by a cloud of particles. Both methods need calibration to transform the quantity of scattered light detected into particle concentration. Photometers are simpler to use and can be directly calibrated to measure mass concentration. However, their response varies not only with aerosol concentration but also with particle size distribution, which frequently contributes to biased measurement. Optical particle counters directly measure the particle number concentration and particle size that allows assessment of the particle mass provided the particles are spherical and of known density. An integrating algorithm is used to calculate the mass concentration of any conventional health-related aerosol fraction. The concentrations calculated thus have been compared with simultaneous measurements by conventional gravimetric sampling to check the possibility of field OPC calibration with real workplace aerosols with a view to further monitoring particle mass concentration. Aerosol concentrations were measured in the food industry using the OPC GRIMM® 1.108 and the CIP 10-Inhalable and CIP 10-Respirable (ARELCO®) aerosol samplers while meat sausages were being brushed and coated with calcium carbonate. Previously, the original OPC inlet had been adapted to sample inhalable aerosol. A mixed aerosol of calcium carbonate and fungi spores was present in the workplace. The OPC particle-size distribution and an estimated average particle density of both aerosol components were used to calculate the mass concentration. The inhalable and respirable aerosol fractions

  11. Workplace aerosol mass concentration measurement using optical particle counters.

    PubMed

    Görner, Peter; Simon, Xavier; Bémer, Denis; Lidén, Göran

    2012-02-01

    Direct-reading aerosol measurement usually uses the optical properties of airborne particles to detect and measure particle concentration. In the case of occupational hygiene, mass concentration measurement is often required. Two aerosol monitoring methods are based on the principle of light scattering: optical particle counting (OPC) and photometry. The former analyses the light scattered by a single particle, the latter by a cloud of particles. Both methods need calibration to transform the quantity of scattered light detected into particle concentration. Photometers are simpler to use and can be directly calibrated to measure mass concentration. However, their response varies not only with aerosol concentration but also with particle size distribution, which frequently contributes to biased measurement. Optical particle counters directly measure the particle number concentration and particle size that allows assessment of the particle mass provided the particles are spherical and of known density. An integrating algorithm is used to calculate the mass concentration of any conventional health-related aerosol fraction. The concentrations calculated thus have been compared with simultaneous measurements by conventional gravimetric sampling to check the possibility of field OPC calibration with real workplace aerosols with a view to further monitoring particle mass concentration. Aerosol concentrations were measured in the food industry using the OPC GRIMM® 1.108 and the CIP 10-Inhalable and CIP 10-Respirable (ARELCO®) aerosol samplers while meat sausages were being brushed and coated with calcium carbonate. Previously, the original OPC inlet had been adapted to sample inhalable aerosol. A mixed aerosol of calcium carbonate and fungi spores was present in the workplace. The OPC particle-size distribution and an estimated average particle density of both aerosol components were used to calculate the mass concentration. The inhalable and respirable aerosol fractions

  12. Contribution of methane to aerosol carbon mass

    NASA Astrophysics Data System (ADS)

    Bianchi, F.; Barmet, P.; Stirnweis, L.; El Haddad, I.; Platt, S. M.; Saurer, M.; Lötscher, C.; Siegwolf, R.; Bigi, A.; Hoyle, C. R.; DeCarlo, P. F.; Slowik, J. G.; Prévôt, A. S. H.; Baltensperger, U.; Dommen, J.

    2016-09-01

    Small volatile organic compounds (VOC) such as methane (CH4) have long been considered non-relevant to aerosol formation due to the high volatility of their oxidation products. However, even low aerosol yields from CH4, the most abundant VOC in the atmosphere, would contribute significantly to the total particulate carbon budget. In this study, organic aerosol (OA) mass yields from CH4 oxidation were evaluated at the Paul Scherrer Institute (PSI) smog chamber in the presence of inorganic and organic seed aerosols. Using labeled 13C methane, we could detect its oxidation products in the aerosol phase, with yields up to 0.09

  13. Mexico City Aerosol Analysis during MILAGRO using High Resolution Aerosol Mass Spectrometry at the Urban Supersite (T0). Part 2: Analysis of the Biomass Burning Contribution and the Modern Carbon Fraction

    SciTech Connect

    Aiken, Allison; de Foy, B.; Wiedinmyer, Christine; DeCarlo, Peter; Ulbrich, Ingrid M.; Wehrli, M. N.; Szidat, S.; Prevot, A. S. H.; Noda, J.; Wacker, L.; Volkamer, Rainer M.; Fortner, Edward; Wang, J. X.; Laskin, Alexander; Shutthanandan, V.; Zheng, J.; Zhang, Renyi; Paredes-Miranda, Guadalupe L.; Arnott, W. P.; Molina, Luis; Sosa, G.; Querol, X.; Jimenez, J. L.

    2010-06-16

    Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Aerosol Mass Spectrometer (AMS) and complementary instrumentation. Positive Matrix Factorization (PMF) of high resolution AMS spectra identified a biomass burning OA (BBOA) component, which includes several large plumes that appear to be from forest fires within the region. Here, we show that the AMS BBOA concentration at T0 correlates with fire counts in the vicinity of Mexico City and that most of the BBOA variability is captured when the FLEXPART model is used for the dispersion of fire emissions as estimated from satellite fire counts. The resulting FLEXPART fire impact index correlates well with the observed BBOA, CH3CN, levoglucosan, and potassium, indicating that wildfires in the region surrounding Mexico City are the dominant source of BBOA at T0 during MILAGRO. The impact of distant BB sources such as the Yucatan is very small during this period. All fire tracers are correlated, with BBOA and levoglucosan showing little background, acetonitrile having a well-known tropospheric background of ~100-150 ppt, and PM2.5 potassium having a background of ~160 ng m-3 (two-thirds of its average concentration), which does not appear to be related to BB sources.

  14. Aerosols, cloud microphysics, and fractional cloudiness.

    PubMed

    Albrecht, B A

    1989-09-15

    Increases in aerosol concentrations over the oceans may increase the amount of low-level cloudiness through a reduction in drizzle-a process that regulates the liquid-water content and the energetics of shallow marine clouds. The resulting increase in the global albedo would be in addition to the increase due to enhancement in reflectivity associated with a decrease in droplet size and would contribute to a cooling of the earth's surface.

  15. Determination of the biogenic secondary organic aerosol fraction in the boreal forest by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Finessi, E.; Decesari, S.; Paglione, M.; Giulianelli, L.; Carbone, C.; Gilardoni, S.; Fuzzi, S.; Saarikoski, S.; Raatikainen, T.; Hillamo, R.; Allan, J.; Mentel, Th. F.; Tiitta, P.; Laaksonen, A.; Petäjä, T.; Kulmala, M.; Worsnop, D. R.; Facchini, M. C.

    2012-01-01

    The study investigates the sources of fine organic aerosol (OA) in the boreal forest, based on measurements including both filter sampling (PM1) and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS) were employed to measure on-line concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions. The NMR results supported the AMS speciation of oxidized organic aerosol (OOA) into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the m/z 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls). Such component, contributing on average 50% of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated with the formation of terrestrial biogenic secondary organic aerosol (BSOA), based on the comparison with spectral profiles obtained from laboratory experiments of terpenes photo-oxidation. The second NMR

  16. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-10-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

  17. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    PubMed Central

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-01-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks. PMID:27733773

  18. Secondary Ion Mass Spectrometry of Environmental Aerosols

    SciTech Connect

    Gaspar, Daniel J.; Cliff, John B.

    2010-08-01

    Atmospheric particles influence many aspects of climate, air quality and human health. Understanding the composition, chemistry and behavior of atmospheric aerosols is a key remaining challenge in improving climate models. Furthermore, particles may be traced back to a particular source based on composition, stable isotope ratios, or the presence of particular surface chemistries. Finally, the characterization of atmospheric particles in the workplace plays an important role in understanding the potential for exposure and environmental and human health effects to engineered and natural nanoscale particles. Secondary ion mass spectrometry (SIMS) is a useful tool in determining any of several aspects of the structure, composition and chemistry of these particles. Often used in conjunction with other surface analysis and electron microscopy methods, SIMS has been used to determine or confirm reactions on and in particles, the presence of particular organic species on the surface of atmospheric aerosols and several other interesting and relevant findings. Various versions of SIMS instruments – dynamic SIMS, time of flight secondary ion mass spectrometry or TOF-SIMS, nanoSIMS – have been used to determine specific aspects of aerosol structure and chemistry. This article describes the strengths of each type of SIMS instrument in the characterization of aerosols, along with guidance on sample preparation, specific characterization specific to the particular information sought in the analysis. Examples and guidance are given for each type of SIMS analysis.

  19. Masses and branching fractions at CDF

    SciTech Connect

    S. D'Auria

    2003-10-30

    The authors present a collection of new results on b-meson and {Lambda}{sub b} masses and branching fractions measured at CDF. They have improved the measurement of the {Lambda}{sub b} and B{sub s} mass and they have measured the branching fractions of B{sub s} {yields} D{sub s}{pi}, {Lambda}{sub b} {yields} {Lambda}{sub c}{pi} and B{sub u} {yields} {Phi}K{sup {+-}}.

  20. 13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan

    NASA Astrophysics Data System (ADS)

    Sebree, Joshua A.; Stern, Jennifer C.; Mandt, Kathleen E.; Domagal-Goldman, Shawn D.; Trainer, Melissa G.

    2016-05-01

    The ratios of the stable isotopes that comprise each chemical species in Titan's atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation - organic aerosol formation and subsequent deposition onto the surface of Titan - has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as 'tholins', via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.

  1. Organic Aerosols in Rural and Remote Atmospheric Environments: Insights from Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Jimenez, J.; Ulbrich, I.; Dunlea, E.; Decarlo, P.; Huffman, A.; Allan, J.; Coe, H.; Alfarra, R.; Canagaratna, M.; Onasch, T.; Jayne, J.; Worsnop, D.; Takami, A.; Miyoshi, T.; Shimono, A.; Hatakeyama, S.; Weimer, S.; Demerjian, K.; Drewnick, F.; Schneider, J.; Middlebrook, A.; Bahreini, R.; Cotrell, L.; Griffin, R.; Leaitch, R.; Li, S.; Hayden, K.; Rautiainen, J.

    2006-12-01

    Organic matter usually accounts for a large fraction of the fine particle mass in rural and remote atmospheres. However, little is known about the sources and properties of this material. Here we report findings on the characteristics and the major types of organic aerosols (OA) in urban downwind, high elevation, forested, and marine atmospheres based on analyses of more than 20 highly time resolved AMS datasets sampled from various locations in the mid-latitude Northern Hemisphere. Organic aerosol components are extracted from these datasets using a custom multiple component mass spectral analysis technique and the Positive Matrix Factorization (PMF) method. These components are evaluated according to their extracted mass spectra and correlations to aerosol species, such as sulfate, nitrate, and elemental carbon, and gas-phase tracer compounds, such as CO and NOx. We have identified a hydrocarbon-like organic aerosol (HOA) component similar in mass spectra to the hydrocarbon substances observed at urban locations. We have also identified several oxygenated OA (OOA) components that show different fragmentation patterns and oxygen to carbon ratios in their mass spectra. Two OOA components a highly oxygenated that has mass spectrum resembling that of fulvic acid (a model compound representative for highly processed/oxidized organics in the environment) and a less oxygenated OOA component, whose spectrum is dominated with ions that are mainly associated with carbonyls and alcohols, are very frequently observed at various rural/remote sites. The oxygenated OOA component is more prevalent at downwind sites influenced by urban transport and the less oxygenated shows correlation to biogenic chamber OA at some locations. Compared to the total OOA concentration, HOA is generally very small and accounts for < 10% of the total OA mass at rural/remote sites. The comparisons between the concentrations of HOA and primary OA (POA) that would be predicted according to inert

  2. Characterization and source apportionment of organic aerosol using offline aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Daellenbach, K. R.; Bozzetti, C.; Křepelová, A.; Canonaco, F.; Wolf, R.; Zotter, P.; Fermo, P.; Crippa, M.; Slowik, J. G.; Sosedova, Y.; Zhang, Y.; Huang, R.-J.; Poulain, L.; Szidat, S.; Baltensperger, U.; Prévôt, A. S. H.; El Haddad, I.

    2015-08-01

    Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make impractical its deployment at sufficient sites to determine regional characteristics. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2.5, PM10) collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g. AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60-91 %) achieved using this technique, together with low detection limits (0.8 μg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon, oxygen containing and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g. filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially-resolved long-term datasets.

  3. Characterization and source apportionment of organic aerosol using offline aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Daellenbach, K. R.; Bozzetti, C.; Křepelová, A.; Canonaco, F.; Wolf, R.; Zotter, P.; Fermo, P.; Crippa, M.; Slowik, J. G.; Sosedova, Y.; Zhang, Y.; Huang, R.-J.; Poulain, L.; Szidat, S.; Baltensperger, U.; El Haddad, I.; Prévôt, A. S. H.

    2016-01-01

    Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make its deployment at sufficient sites to determine regional characteristics impractical. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2.5, and PM10, i.e., PM with aerodynamic diameters smaller than 1, 2.5, and 10 µm, respectively), collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g., AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60-91 %) achieved using this technique, together with low detection limits (0.8 µg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon ions, ions containing oxygen, and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning, and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g., filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially resolved long-term data sets.

  4. Characterization of aerosol composition, concentrations, and sources at Baengnyeong Island, Korea using an aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Lee, Taehyoung; Choi, Jinsoo; Lee, Gangwoong; Ahn, Junyoung; Park, Jin Soo; Atwood, Samuel A.; Schurman, Misha; Choi, Yongjoo; Chung, Yoomi; Collett, Jeffrey L.

    2015-11-01

    To improve understanding of the sources and chemical properties of particulate pollutants on the western side of the Korean Peninsula, an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) measured non-refractory fine (PM1) particles from May to November, 2011 at Baengnyeong Island, South Korea. Organic matter and sulfate were generally the most abundant species and exhibited maximum concentrations of 36 μg/m3 and 39 μg/m3, respectively. Nitrate concentrations peaked at 32 μg/m3 but were typically much lower than sulfate and organic matter concentrations. May, September, October, and November featured the highest monthly average concentrations, with lower concentrations typically observed from June through August. Potential source contribution function (PSCF) analysis and individual case studies revealed that transport from eastern China, an area with high SO2 emissions, was associated with high particulate sulfate concentrations at the measurement site. Observed sulfate aerosol sometimes was fully neutralized by ammonium but often was acidic; the average ammonium to sulfate molar ratio was 1.49. Measured species size distributions revealed a range of sulfate particle size distributions with modes between 100 and 600 nm. Organic aerosol source regions were widespread, including contributions from eastern China and South Korea. Positive matrix factorization (PMF) analysis indicated three "factors," or types of organic aerosol, comprising one primary, hydrocarbon-like organic aerosol (HOA) and two oxidized organic aerosol (OOA) components, including a more oxidized (MO-OOA) and a less oxidized (LO-OOA) oxidized organic aerosol. On average, HOA and OOA contributed 21% and 79% of the organic mass (OM), respectively, with the MO-OOA fraction nearly three times as abundant as the LO-OOA fraction. Biomass burning contributions to observed OM were low during the late spring/early summer agricultural burning season in eastern China, since

  5. Stable Carbon Fractionation In Size Segregated Aerosol Particles Produced By Controlled Biomass Burning

    NASA Astrophysics Data System (ADS)

    Masalaite, Agne; Garbaras, Andrius; Garbariene, Inga; Ceburnis, Darius; Martuzevicius, Dainius; Puida, Egidijus; Kvietkus, Kestutis; Remeikis, Vidmantas

    2014-05-01

    Biomass burning is the largest source of primary fine fraction carbonaceous particles and the second largest source of trace gases in the global atmosphere with a strong effect not only on the regional scale but also in areas distant from the source . Many studies have often assumed no significant carbon isotope fractionation occurring between black carbon and the original vegetation during combustion. However, other studies suggested that stable carbon isotope ratios of char or BC may not reliably reflect carbon isotopic signatures of the source vegetation. Overall, the apparently conflicting results throughout the literature regarding the observed fractionation suggest that combustion conditions may be responsible for the observed effects. The purpose of the present study was to gather more quantitative information on carbonaceous aerosols produced in controlled biomass burning, thereby having a potential impact on interpreting ambient atmospheric observations. Seven different biomass fuel types were burned under controlled conditions to determine the effect of the biomass type on the emitted particulate matter mass and stable carbon isotope composition of bulk and size segregated particles. Size segregated aerosol particles were collected using the total suspended particle (TSP) sampler and a micro-orifice uniform deposit impactor (MOUDI). The results demonstrated that particle emissions were dominated by the submicron particles in all biomass types. However, significant differences in emissions of submicron particles and their dominant sizes were found between different biomass fuels. The largest negative fractionation was obtained for the wood pellet fuel type while the largest positive isotopic fractionation was observed during the buckwheat shells combustion. The carbon isotope composition of MOUDI samples compared very well with isotope composition of TSP samples indicating consistency of the results. The measurements of the stable carbon isotope ratio in

  6. Factor analysis of combined organic and inorganic aerosol mass spectra from high resolution aerosol mass spectrometer measurements

    NASA Astrophysics Data System (ADS)

    Sun, Y. L.; Zhang, Q.; Schwab, J. J.; Yang, T.; Ng, N. L.; Demerjian, K. L.

    2012-09-01

    Positive matrix factorization (PMF) was applied to the merged high resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer (AMS) measurements to investigate the sources and evolution processes of submicron aerosols in New York City in summer 2009. This new approach is able to study the distribution of organic and inorganic species in different types of aerosols, the acidity of organic aerosol (OA) factors, and the fragment ion patterns related to photochemical processing. In this study, PMF analysis of the unified AMS spectral matrix resolved 8 factors. The hydrocarbon-like OA (HOA) and cooking OA (COA) factors contain negligible amounts of inorganic species. The two factors that are primarily ammonium sulfate (SO4-OA) and ammonium nitrate (NO3-OA), respectively, are overall neutralized. Among all OA factors the organic fraction of SO4-OA shows the highest degree of oxidation (O/C = 0.69). Two semi-volatile oxygenated OA (OOA) factors, i.e., a less oxidized (LO-OOA) and a more oxidized (MO-OOA), were also identified. MO-OOA represents local photochemical products with a diurnal profile exhibiting a pronounced noon peak, consistent with those of formaldehyde (HCHO) and Ox(= O3 + NO2). The NO+/NO2+ ion ratio in MO-OOA is much higher than that in NO3-OA and in pure ammonium nitrate, indicating the formation of organic nitrates. The nitrogen-enriched OA (NOA) factor contains ~25% of acidic inorganic salts, suggesting the formation of secondary OA via acid-base reactions of amines. The size distributions of OA factors derived from the size-resolved mass spectra show distinct diurnal evolving behaviors but overall a progressing evolution from smaller to larger particle mode as the oxidation degree of OA increases. Our results demonstrate that PMF analysis of the unified aerosol mass spectral matrix which contains both inorganic and organic aerosol signals may enable the deconvolution of more OA factors and gain more insights into the

  7. Nitrogen isotopic fractionation during plasma synthesis of Titan's aerosols analogues

    NASA Astrophysics Data System (ADS)

    Kuga, M.; Carrasco, N.; Marty, B.; Marrocchi, Y.; Bernard, S.; Rigaudier, T.

    2013-12-01

    The Cassini-Huygens mission recently provided measurements of the abundance of nitrogen isotopes in Titan's atmosphere. The 14N/15N ratio in the two most abundant N-bearing molecules in Titan's atmosphere was found to be 183×5 for N2 [1] and 56×8 for HCN [2]. Those two molecules are greatly enriched in the heavier isotope 15N compared to our terrestrial atmosphere and Titan's HCN is about three times richer in 15N than its potential photochemical precursor N2. This implies an important fractionation process in the HCN production chain, which is tentatively attributed to an isotopic selectivity of the photodissociation of N2 in Titan's ionosphere [3-4]. The organic aerosols, forming the Titan's orange characteristic haze layers, also contain large amounts of nitrogen [5], and thus represent a third important nitrogen reservoir in Titan's atmosphere. These organic aerosols are presumably produced in the upper atmosphere by chemical reactions between N2 and CH4 induced by solar radiation and electron bombardment from Saturn's magnetosphere. As HCN is a possible precursor for aerosol polymerization [6-7], the 15N enrichment observed in HCN may be linked to the polymerization process. Unfortunately, no data exists on the isotopic nitrogen abundance in Titan's aerosols, and this question remains open. To address this issue, laboratory aerosols analogues have been produced in a N2-CH4 plasma and their nitrogen isotopic composition have been investigated. In this study, the experimental aerosols, called " tholins ", have been synthetized in the PAMPRE reactor (LATMOS, France). This setup is dedicated to simulate chemical processes occurring in Titan's atmosphere and consists in an RF plasma discharge initiated in a N2-CH4 gas mixture at room temperature [8-9]. For our purpose, tholins were produced at different initial CH4 percentages (1, 2, 5, 10%), representative of the variation of the CH4 concentration in Titan's atmosphere. 15N/14N ratio of the N2 gas used in the

  8. Characterization of ice-nucleating bacteria using on-line electron impact ionization aerosol mass spectrometry.

    PubMed

    Wolf, R; Slowik, J G; Schaupp, C; Amato, P; Saathoff, H; Möhler, O; Prévôt, A S H; Baltensperger, U

    2015-04-01

    The mass spectral signatures of airborne bacteria were measured and analyzed in cloud simulation experiments at the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) facility. Suspensions of cultured cells in pure water were sprayed into the aerosol and cloud chambers forming an aerosol which consisted of intact cells, cell fragments and residual particles from the agar medium in which the bacteria were cultured. The aerosol particles were analyzed with a high-resolution time-of-flight aerosol mass spectrometer equipped with a newly developed PM2.5 aerodynamic lens. Positive matrix factorization (PMF) using the multilinear engine (ME-2) source apportionment was applied to deconvolve the bacteria and agar mass spectral signatures. The bacteria mass fraction contributed between 75 and 95% depending on the aerosol generation, with the remaining mass attributed to agar. We present mass spectra of Pseudomonas syringae and Pseudomonas fluorescens bacteria typical for ice-nucleation active bacteria in the atmosphere to facilitate the distinction of airborne bacteria from other constituents in ambient aerosol, e.g. by PMF/ME-2 source apportionment analyses. Nitrogen-containing ions were the most salient feature of the bacteria mass spectra, and a combination of C4 H8 N(+) (m/z 70) and C5 H12 N(+) (m/z 86) may be used as marker ions. PMID:26149110

  9. Influence of measurement uncertainties on fractional solubility of iron in mineral aerosols over the oceans

    NASA Astrophysics Data System (ADS)

    Meskhidze, Nicholas; Johnson, Matthew S.; Hurley, David; Dawson, Kyle

    2016-09-01

    The atmospheric supply of mineral dust iron (Fe) plays a crucial role in the Earth's biogeochemical cycle and is of specific importance as a micronutrient in the marine environment. Observations show several orders of magnitude variability in the fractional solubility of Fe in mineral dust aerosols, making it hard to assess the role of mineral dust in the global ocean biogeochemical Fe cycle. In this study we compare the operational solubility of mineral dust aerosol Fe associated with the flow-through leaching protocol to the results of the global 3-D chemical transport model GEOS-Chem. According to the protocol, aerosol Fe is defined as soluble by first deionized water leaching of mineral dust through a 0.45 μm pore size membrane followed by acidification and storage of the leachate over a long period of time prior to analysis. To estimate the uncertainty in soluble Fe results introduced by the flow-through leaching protocol, we prescribe an average 50% (range of 30-70%) fractional solubility to sub-0.45 μm sized mineral dust particles that may inadvertently pass the filter and end up in the acidified (at pH ∼ 1.7) leachate for a couple of month period. In the model, the fractional solubility of Fe is either explicitly calculated using a complex mineral aerosol Fe dissolution equations, or prescribed to be 1% and 4% often used by global ocean biogeochemical Fe cycle models to reproduce the broad characteristics of the presently observed ocean dissolved iron distribution. Calculations show that the fractional solubility of Fe derived through the flow-through leaching is higher compared to the model results. The largest differences (∼40%) are predicted to occur farther away from the dust source regions, over the areas where sub-0.45 μm sized mineral dust particles contribute a larger fraction of the total mineral dust mass. This study suggests that different methods used in soluble Fe measurements and inconsistences in the operational definition of

  10. Determination of the biogenic secondary organic aerosol fraction in the boreal forest by AMS and NMR measurements

    NASA Astrophysics Data System (ADS)

    Finessi, E.; Decesari, S.; Paglione, M.; Giulianelli, L.; Carbone, C.; Gilardoni, S.; Fuzzi, S.; Saarikoski, S.; Raatikainen, T.; Hillamo, R.; Allan, J.; Mentel, Th. F.; Tiitta, P.; Laaksonen, A.; Petäjä, T.; Kulmala, M.; Worsnop, D. R.; Facchini, M. C.

    2011-08-01

    The study investigates the sources of fine organic aerosol (OA) in the boreal forest, based on measurements including both filter sampling (PM1) and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS) were employed to measure on-line air mass concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions. The NMR results supported the AMS speciation of oxidized organic aerosol (OOA) into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the m/z 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls). Such component, contributing on average 50 % of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component showed features consistent with less oxygenated aerosols and was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated to the formation of terrestrial biogenic secondary organic aerosol (BSOA), based on the comparison with spectral profiles obtained from

  11. Chemical Analysis of Fractionated Halogens in Atmospheric Aerosols Collected in Okinawa, Japan

    NASA Astrophysics Data System (ADS)

    Tsuhako, A.; Miyagi, Y.; Somada, Y.; Azechi, S.; Handa, D.; Oshiro, Y.; Murayama, H.; Arakaki, T.

    2013-12-01

    Halogens (Cl, Br and I) play important roles in the atmosphere, e.g. ozone depletion by Br during spring in Polar Regions. Sources of halogens in atmospheric aerosols are mainly from ocean. But, for example, when we analyzed Br- with ion chromatography, its concentrations were almost always below the detection limit, which is also much lower than the estimated concentrations from sodium ion concentrations. We hypothesized that portions of halogens are escaped to the atmosphere, similar to chlorine loss, changed their chemical forms to such as BrO3- and IO3-, and/or even formed precipitates. There was few reported data so far about fractionated halogen concentrations in atmospheric aerosols. Thus, purpose of this study was to determine halogen concentrations in different fractions; free ion, water-soluble chemically transformed ions and precipitates using the authentic aerosols. Moreover, we analyzed seasonal variation for each fraction. Atmospheric aerosol samples were collected at Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS) of Okinawa, Japan during January 2010 and August 2013. A high volume air sampler was used for collecting total particulate matters on quartz filters on a weekly basis. Ultrapure water was used to extract water-soluble factions of halogens. The extracted solutions were filtered with the membrane filter and used for chemical analysis with ion chromatography and ICP-MS. Moreover, the total halogens in aerosols were obtained after digesting aerosols with tetramethylammonium hydroxide (TMAH) using the microwave and analysis with ICP-MS. For Cl, water-soluble Cl- accounted for about 70% of the estimates with Na content. No other forms of water-soluble Cl were found. About 30% of Cl was assumed volatilized to the gas-phase. For Br, water-soluble Br accounted for about 43% of the estimates with Na content, and within the 43%, about 10% of Br was not in the form of Br-. About 46% of Br was assumed volatilized to the gas-phase. For I

  12. Characterization of aerosol composition and sources in the greater Atlanta area by aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Ng, N. L.; Xu, L.; Suresh, S.; Weber, R. J. J.; Baumann, K.; Edgerton, E. S.

    2014-12-01

    An important and uncertain aspect of biogenic secondary organic aerosol (SOA) formation is that it is often associated with anthropogenic pollution tracers. Prior studies in Atlanta suggested that 70-80% of the carbon in water-soluble organic carbon (WSOC) is modern, yet it is well-correlated with the anthropogenic CO. In this study, we deployed a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) at multiple sites in different seasons (May 2012-February 2013) to characterize the sources and chemical composition of aerosols in the greater Atlanta area. This area in the SE US is ideal to investigate anthropogenic-biogenic interactions due to high natural and anthropogenic emissions. These extensive field studies are part of the Southeastern Center for Air Pollution and Epidemiology study (SCAPE). The HR-ToF-AMS is deployed at four sites (~ 3 weeks each) in rotation: Jefferson Street (urban), Yorkville (rural), roadside site (near Highway 75/85), and Georgia Tech site (campus), with the urban and rural sites being part of the SEARCH network. We obtained seven HR-ToF-AMS datasets in total. During the entire measurement period, the ACSM is stationary at the GIT site and samples continuously. We perform positive matrix factorization (PMF) analysis on the HR-ToF-AMS and ACSM data to deconvolve the OA into different components. While the diurnal cycle of the total OA is flat as what have been previously observed, the OA factors resolved by PMF analysis show distinctively different diurnal trends. We find that the "more-oxidized oxygenated OA" (MO-OOA) constitutes a major fraction of OA at all sites. In summer, OA is dominated by SOA, e.g., isoprene-OA and OOA with different degrees of oxidation. In contrary, biomass burning OA is more prominent in winter data. By comparing HR-ToF-AMS and ACSM data during the same sampling periods, we find that the aerosol time series are highly correlated, indicating the

  13. Oxygen Isotope Anomaly in the Carbonate Fractions of Aerosols and its Potential to Assess Urban Pollution

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Abramian, A.; Dominguez, G.; Jackson, T.; Thiemens, M. H.

    2008-12-01

    Mineral dust is emitted into the atmosphere from arid regions in Asia yearly, accounting for ~36% of global aerosol emissions, 5900 Tg yr-1 [IPCC 2007]. Increasing anthropogenic emissions and persistent dust emissions not only have reduced the air quality in Asia itself, but are also affecting the pollutant deposition into the Pacific Ocean and air quality in downwind areas. The carbonate component of mineral dust (calcite (CaCO3) and dolomite (CaMg(CO3)2) is particularly reactive and can comprise as much as 30% of the total mineral dust aerosol, depending on the source region [Claquin et al., 1999]. Carbonate can affect atmospheric chemical processes and aerosol characteristics because the acid neutralizing capacity of this species facilitates the heterogeneous conversion of sulphate and nitrate. Understanding heterogeneous reactions occurring on the surface of aerosol particles will lead to a better understanding of the fate and transport of molecules in the troposphere as well as to resolve their role in air quality and pollution. The primary goal of this work is to develop an isotope methodology for carbonates that can be used as a chemical marker for the origin of polluted air plumes and chemical transformation during the long range transport of air masses. We will discuss the carbon and oxygen isotope composition of the CO2 released from the fine (< 1 μm) and coarse (> 1 μm) particles collected at two different sites [Mt. Soledad (800 ft) and Scripps Pier, La Jolla, California] and its possible utility as a tracer to identify the long-range transport of aerosol from local pollution events. The degree of urban influence of sampled air parcels at each site was quantified through back-trajectory analysis of NOAA HYSPLIT output data. Interestingly, the isotopes of oxygen did not follow standard mass dependent relationship (δ17O ~ 0.52 δ18O) rather have excess 17O (Δ17O = δ17O- 0.52δ18O) ranging from 0.9 to 3.9 per mil. A highly significant correlation (r2

  14. OMI tropospheric NO2 air mass factors over South America: effects of biomass burning aerosols

    NASA Astrophysics Data System (ADS)

    Castellanos, P.; Boersma, K. F.; Torres, O.; de Haan, J. F.

    2015-03-01

    Biomass burning is an important and uncertain source of aerosols and NOx (NO + NO2) to the atmosphere. OMI observations of tropospheric NO2 are essential for characterizing this emissions source, but inaccuracies in the retrieval of NO2 tropospheric columns due to the radiative effects of aerosols, especially light-absorbing carbonaceous aerosols, are not well understood. It has been shown that the O2-O2 effective cloud fraction and pressure retrieval is sensitive to aerosol optical and physical properties, including aerosol optical depth (AOD). Aerosols implicitly influence the tropospheric air mass factor (AMF) calculations used in the NO2 retrieval through the effective cloud parameters used in the independent pixel approximation. In this work, we explicitly account for the effects of biomass burning aerosols in the tropospheric NO2 AMF calculation by including collocated aerosol extinction vertical profile observations from the CALIOP instrument, and aerosol optical depth (AOD) and single scattering albedo (SSA) retrieved by the OMI near-UV aerosol algorithm (OMAERUV) in the DISAMAR radiative transfer model for cloud-free scenes. Tropospheric AMFs calculated with DISAMAR were benchmarked against AMFs reported in the Dutch OMI NO2 (DOMINO) retrieval; the mean and standard deviation (SD) of the difference was 0.6 ± 8%. Averaged over three successive South American biomass burning seasons (2006-2008), the spatial correlation in the 500 nm AOD retrieved by OMI and the 532 nm AOD retrieved by CALIOP was 0.6, and 72% of the daily OMAERUV AOD observations were within 0.3 of the CALIOP observations. Overall, tropospheric AMFs calculated with observed aerosol parameters were on average 10% higher than AMFs calculated with effective cloud parameters. For effective cloud radiance fractions less than 30%, or effective cloud pressures greater than 800 hPa, the difference between tropospheric AMFs based on implicit and explicit aerosol parameters is on average 6 and 3

  15. A two-sided fractional conservation of mass equation

    NASA Astrophysics Data System (ADS)

    Olsen, Jeffrey S.; Mortensen, Jeff; Telyakovskiy, Aleksey S.

    2016-05-01

    A two-sided fractional conservation of mass equation is derived by using left and right fractional Mean Value Theorems. This equation extends the one-sided fractional conservation of mass equation of Wheatcraft and Meerschaert. Also, a two-sided fractional advection-dispersion equation is derived. The derivations are based on Caputo fractional derivatives.

  16. Enhancements of the refractory submicron aerosol fraction in the Arctic polar vortex: feature or exception?

    NASA Astrophysics Data System (ADS)

    Weigel, R.; Volk, C. M.; Kandler, K.; Hösen, E.; Günther, G.; Vogel, B.; Grooß, J.-U.; Khaykin, S.; Belyaev, G. V.; Borrmann, S.

    2014-11-01

    In situ measurements with a four-channel stratospheric condensation particle counter (CPC) were conducted at up to 20 km altitude on board the aircraft M-55 Geophysica from Kiruna, Sweden, in January through March (EUPLEX 2003, RECONCILE 2010) and in December (ESSenCe 2011). During all campaigns air masses from the upper stratosphere and mesosphere were subsiding inside the Arctic winter vortex, thus initializing a transport of refractory aerosol into the lower stratosphere (Θ < 500 K). The strength and extent of this downward transport varied between the years depending on the dynamical evolution of the vortex. Inside the vortex and at potential temperatures Θ ≥ 450 K around 11 submicron particles per cm3 were generally detected. Up to 8 of these 11 particles per cm3 were found to contain thermo-stable (at 250 °C) residuals with diameters of 10 nm to about 1 μm. Particle mixing ratios (150 mg-1) and fractions of non-volatile particles (75% of totally detected particles) exhibited highest values in air masses having the lowest content of nitrous oxide (70 nmol mol-1 of N2O). This indicates that refractory aerosol originates from the upper stratosphere or the mesosphere. Derived from the mixing ratio of the simultaneously measured long-lived tracer N2O, an empirical index serves to differentiate probed air masses according to their origin: inside the vortex, the vortex edge region, or outside the vortex. Previously observed high fractions of refractory submicron aerosol in the 2003 Arctic vortex were ascribed to unusually strong subsidence during that winter. However, measurements under perturbed vortex conditions in 2010 and during early winter in December 2011 revealed similarly high values. Thus, the abundance of refractory aerosol in the lower stratosphere within the Arctic vortices appears to be a regular feature rather than the exception. During December, the import from aloft into the lower stratosphere appears to be developing; thereafter the abundance

  17. Mass Fractionation Laws, Mass-Independent Effects, and Isotopic Anomalies

    NASA Astrophysics Data System (ADS)

    Dauphas, Nicolas; Schauble, Edwin A.

    2016-06-01

    Isotopic variations usually follow mass-dependent fractionation, meaning that the relative variations in isotopic ratios scale with the difference in mass of the isotopes involved (e.g., δ17O ≈ 0.5×δ18O). In detail, however, the mass dependence of isotopic variations is not always the same, and different natural processes can define distinct slopes in three-isotope diagrams. These variations are subtle, but improvements in analytical capabilities now allow precise measurement of these effects and make it possible to draw inferences about the natural processes that caused them (e.g., reaction kinetics versus equilibrium isotope exchange). Some elements, in some sample types, do not conform to the regularities of mass-dependent fractionation. Oxygen and sulfur display a rich phenomenology of mass-independent fractionation, documented in the laboratory, in the rock record, and in the modern atmosphere. Oxygen in meteorites shows isotopic variations that follow a slope-one line (δ17O ≈ δ18O) whose origin may be associated with CO photodissociation. Sulfur mass-independent fractionation in ancient sediments provides the tightest constraint on the oxygen partial pressure in the Archean and the timing of Earth's surface oxygenation. Heavier elements also show departures from mass fractionation that can be ascribed to exotic effects associated with chemical reactions such as magnetic effects (e.g., Hg) or the nuclear field shift effect (e.g., U or Tl). Some isotopic variations in meteorites and their constituents cannot be related to the terrestrial composition by any known process, including radiogenic, nucleogenic, and cosmogenic effects. Those variations have a nucleosynthetic origin, reflecting the fact that the products of stellar nucleosynthesis were not fully homogenized when the Solar System formed. Those anomalies are found at all scales, from nanometer-sized presolar grains to bulk terrestrial planets. They can be used to learn about stellar

  18. Some Technical Aspects of a CALIOP and MODIS Data Analysis that Examines Near-Cloud Aerosol Properties as a Function of Cloud Fraction

    NASA Technical Reports Server (NTRS)

    Varnai, Tamas; Yang, Weidong; Marshak, Alexander

    2016-01-01

    CALIOP shows stronger near-cloud changes in aerosol properties at higher cloud fractions. Cloud fraction variations explain a third of near-cloud changes in overall aerosol statistics. Cloud fraction and aerosol particle size distribution have a complex relationship.

  19. Comparison of particle lung doses from the fine and coarse fractions of urban PM-10 aerosols.

    PubMed

    Venkataraman, C; Kao, A S

    1999-02-01

    The U.S. Environmental Protection Agency (EPA) recently revised the national ambient air quality standards to include a new PM-2.5 particulate standard. We examine the contributions of fine (PM-2.5) and coarse (PM-2.5 to -10) fraction of typical urban aerosols to particle doses in different lung airways resulting from 24-h exposure to the standard concentration of 150 microg m-3. The aerosol is assumed to have a bimodal lognormal mass distribution with mass median diameters of 0.2 and 5 microm, and geometric standard deviation of 1.7 and 57% of the mass in the fine (PM-2.5) mode. The daily mass dose from exposure to 150 microg m-3 of PM-10 in the nasopharyngeal (NPL) region is 20-51 microg day-1 (1.5% of inhaled fines) and 377-687 microg day-1 (30% of inhaled coarse), respectively, of fine and coarse mass filtered in the nose. Similar daily mass doses from fine and coarse fractions, respectively, to the tracheobronchial (TBL) region are 28-38 (1.5%) and 40-52 (4%) microg day-1 and to the pulmonary (PUL) region are 18-194 (6%) and 32-55 microg day-1 (2%). The daily number dose in the NPL region is 5-15 x 10(8) (0.06% of inhaled fines) and 5-10 x 10(6) day-1 (13% of inhaled coarse) respectively, of fine and coarse particles. Similar number doses to the TBL region are 2.2-3.1 x 10(10) (2%) and 7.1-11. 1 x 10(5) (2%) day-1 and to the PUL region are 1.6-16.7 x 10(10) (9%) and 2.9-17.0 x 10(5) (3%) day-1. The daily surface mass dose (microg cm-2 day-1) from coarse fraction particles is large in generations 3-5. The daily number dose (particles day-1) and surface number dose (particles cm-2 day-1) are higher from the fine than the coarse fraction, by about 10(3) to 10(5) times in all lung airways. Fine fraction particles result in 10,000 times greater particle number dose per macrophage than coarse fraction particles. Particle number doses do not follow trends in mass doses, are much larger from fine than coarse fraction, and must be considered in assessing PM health

  20. Organic compounds present in the natural Amazonian aerosol: Characterization by gas chromatography-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Graham, Bim; Guyon, Pascal; Taylor, Philip E.; Artaxo, Paulo; Maenhaut, Willy; Glovsky, M. Michael; Flagan, Richard C.; Andreae, Meinrat O.

    2003-12-01

    As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)-Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign in July 2001, separate day and nighttime aerosol samples were collected at a ground-based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural "background" aerosol. We used a high-volume sampler to separate the aerosol into fine (aerodynamic diameter, AD < 2.5 μm) and coarse (AD > 2.5 μm) size fractions and quantified a range of organic compounds in methanolic extracts of the samples by a gas chromatographic-mass spectrometric technique. The carbon fraction of the compounds could account for an average of 7% of the organic carbon (OC) in both the fine and coarse aerosol fractions. We observed the highest concentrations of sugars, sugar alcohols, and fatty acids in the coarse aerosol samples, which suggests that these compounds are associated with primary biological aerosol particles (PBAP) observed in the forest atmosphere. Of these, trehalose, mannitol, arabitol, and the fatty acids were found to be more prevalent at night, coinciding with a nocturnal increase in PBAP in the 2-10 μm size range (predominantly yeasts and other small fungal spores). In contrast, glucose, fructose, and sucrose showed persistently higher daytime concentrations, coinciding with a daytime increase in large fungal spores, fern spores, pollen grains, and, to a lesser extent, plant fragments (generally >20 μm in diameter), probably driven by lowered relative humidity and enhanced wind speeds/convective activity during the day. For the fine aerosol samples a series of dicarboxylic and hydroxyacids were detected with persistently higher daytime concentrations, suggesting that photochemical production of a secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Anhydrosugars (levoglucosan, mannosan, galactosan), which are

  1. CALIPSO Observations of Near-Cloud Aerosol Properties as a Function of Cloud Fraction

    NASA Technical Reports Server (NTRS)

    Yang, Weidong; Marshak, Alexander; Varnai, Tamas; Wood, Robert

    2015-01-01

    This paper uses spaceborne lidar data to study how near-cloud aerosol statistics of attenuated backscatter depend on cloud fraction. The results for a large region around the Azores show that: (1) far-from-cloud aerosol statistics are dominated by samples from scenes with lower cloud fractions, while near-cloud aerosol statistics are dominated by samples from scenes with higher cloud fractions; (2) near-cloud enhancements of attenuated backscatter occur for any cloud fraction but are most pronounced for higher cloud fractions; (3) the difference in the enhancements for different cloud fractions is most significant within 5km from clouds; (4) near-cloud enhancements can be well approximated by logarithmic functions of cloud fraction and distance to clouds. These findings demonstrate that if variability in cloud fraction across the scenes used to composite aerosol statistics are not considered, a sampling artifact will affect these statistics calculated as a function of distance to clouds. For the Azores-region dataset examined here, this artifact occurs mostly within 5 km from clouds, and exaggerates the near-cloud enhancements of lidar backscatter and color ratio by about 30. This shows that for accurate characterization of the changes in aerosol properties with distance to clouds, it is important to account for the impact of changes in cloud fraction.

  2. Ultrahigh resolution mass spectrometric characterization of organic aerosol from European and Chinese cities

    NASA Astrophysics Data System (ADS)

    Wang, Kai; Huang, Ru-Jin; Hoffmann, Thorsten

    2016-04-01

    Organic aerosol constitutes a substantial fraction (20-90%) of submicrometer aerosol mass, playing an important role in air quality and human health. Over the past few years, ultra-high resolution mass spectrometry (UHRMS) has been applied to elucidate the chemical composition of ambient aerosols. However, most of the UHRMS studies used direct infusion without prior separation by liquid chromatography, which may cause the loss of individual compound information and interference problems. In the present study, urban ambient aerosol with particle diameter < 2.5 μm was collected in Mainz, Germany and Beijing, China, respectively. Two pretreatment procedures were applied to extract the organic compounds from the filter samples: One method uses a mixture of acetonitrile and water, the other uses pure water and prepared for the extraction of humic-like substances. The extracts were analyzed by ultra-high-performance liquid chromatography coupled with an Orbitrap mass spectrometer in both negative and the positive modes. The effects of pretreatment procedures on the characterization of organic aerosol and the city-wise difference in chemical composition of organic aerosol will be discussed in detail.

  3. ANALYSIS OF RESPIRATORY DESPOSITION DOSE OF INHALED AMBIENT AEROSOLS FOR DIFFERENT SIZE FRACTIONS

    EPA Science Inventory

    ANALYSIS OF RESPIRATORY DEPOSITION DOSE OF INHALED AMBIENT AEROSOLS FOR DIFFERENT SIZE FRACTIONS. Chong S. Kim, SC. Hu**, PA Jaques*, US EPA, National Health and Environmental Effects Research Laboratory, Research Triangle Park, NC 27711; **IIT Research Institute, Chicago, IL; *S...

  4. Non-Refractory Submicron Aerosol Mass Loadings during NEAQS

    NASA Astrophysics Data System (ADS)

    Middlebrook, A. M.; Matthew, B. M.; Canagaratna, M. R.; Worsnop, D. R.; Quinn, P. K.; Degouw, J. A.; Warneke, C.; Goldan, P. D.; Kuster, W. C.; Williams, E. J.; McKeen, S. A.

    2003-12-01

    During the New England Air Quality Study (NEAQS) in July-August 2002, an Aerosol Mass Spectrometer (AMS) was deployed aboard the NOAA ship RONALD H. BROWN and collected 2-minute averaged data. The AMS, which measures non-refractory components of aerosol particles with aerodynamic diameters between roughly 40 and 1500 nm, produced particle mass spectra as well as aerosol organic, sulfate, ammonium, and nitrate mass distributions. A wide variety of air masses were sampled, including clean marine, clean continental, and polluted continental air masses. In general, the volatile particle composition was mostly organic and sulfate with lesser amounts of ammonium and nitrate and the mass loadings typically peaked around 400-600 nm in vacuum aerodynamic diameter. Although the AMS sulfate and ammonium concentrations were highly correlated with the sulfate and ammonium concentrations from the Particle into Liquid (PILS) instrument also deployed on the ship, the AMS and PILS nitrate concentrations were not correlated and at times anti-correlated. In contrast, the AMS nitrate and organic concentrations as well as the AMS nitrate and gas phase alkyl nitrate concentrations were highly correlated. These results suggest that organic nitrate was present in the submicron aerosol phase. The AMS organic concentrations were generally higher than the AMS sulfate concentrations, consistent with other shipboard measurements. Whenever the sulfate concentration increased, the organic concentration also increased, indicating that sulfate and organic aerosol growth are influenced by the same processes or that sulfate may play a role in organic aerosol growth. The exception to this pattern occurred during a sea fog event where the sulfate concentration increased and the organic concentration decreased, probably due to rapid aqueous phase sulfur oxidation and relatively less oxidation of organic compounds. Furthermore, the organic concentration often increased without concurrent increases in

  5. Molecular composition of the water-soluble fraction of atmospheric carbonaceous aerosols collected during ACE-Asia

    NASA Astrophysics Data System (ADS)

    Mader, B. T.; Yu, J. Z.; Xu, J. H.; Li, Q. F.; Wu, W. S.; Flagan, R. C.; Seinfeld, J. H.

    2004-03-01

    During the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia), samples of carbonaceous aerosols were collected on board the Center for Interdisciplinary Remotely Piloted Aircraft Studies (CIRPAS) De Havilland DHC-6 Twin Otter aircraft. The samples were analyzed to determine their total carbon (TC) and water-soluble organic compound (WSOC) contents as well as to identify the individual compounds comprising the WSOC fraction of the aerosol. The TC concentrations varied from 3.5 to 14.3 μg C m-3; the highest TC levels were observed for samples collected in pollution layers that originated over mainland China. WSOC concentrations ranged from 0.54 to 7.2 μg C m-3, with the WSOC fraction contributing from 10 to 50% of the carbon mass. About 50% of the carbonaceous aerosol mass in pollution layers could be attributed to WSOC. For samples collected in dust layers the WSOC fraction of TC was much lower than that observed in pollution layers. The sum of all the detected organic ions accounted for 6.9-19% of the WSOC. In the six samples collected by the Twin Otter during ACE-Asia, of the organic ions identified in the WSOC fraction, oxalate had the highest concentration. Samples collected from pollution layers exhibited a slightly higher ratio of formate to oxalate as compared to the other samples. Two samples had a relatively high ratio of lactate to oxalate, which might be a signature of some currently unidentified source of carbonaceous aerosol. The sum of the masses of sulfate and nitrate ions exceeded the sum of the masses of the identified organic ions by a factor of 9 to 17. The chemical levoglucosan, a tracer for biomass burning, comprised from 0.1 to 0.4% of TC mass. Comparing this ratio to the ratio measured directly in wood-burning studies it was determined that biomass burning may have represented from ≈2 to 10% of the carbonaceous aerosol collected during ACE-Asia.

  6. Wintertime aerosol chemical composition and source apportionment of the organic fraction in the metropolitan area of Paris

    NASA Astrophysics Data System (ADS)

    Crippa, M.; DeCarlo, P. F.; Slowik, J. G.; Mohr, C.; Heringa, M. F.; Chirico, R.; Poulain, L.; Freutel, F.; Sciare, J.; Cozic, J.; Di Marco, C. F.; Elsasser, M.; Nicolas, J. B.; Marchand, N.; Abidi, E.; Wiedensohler, A.; Drewnick, F.; Schneider, J.; Borrmann, S.; Nemitz, E.; Zimmermann, R.; Jaffrezo, J.-L.; Prévôt, A. S. H.; Baltensperger, U.

    2013-01-01

    The effect of a post-industrial megacity on local and regional air quality was assessed via a month-long field measurement campaign in the Paris metropolitan area during winter 2010. Here we present source apportionment results from three aerosol mass spectrometers and two aethalometers deployed at three measurement stations within the Paris region. Submicron aerosol composition is dominated by the organic fraction (30-36%) and nitrate (28-29%), with lower contributions from sulfate (14-16%), ammonium (12-14%) and black carbon (7-13%). Organic source apportionment was performed using positive matrix factorization, resulting in a set of organic factors corresponding both to primary emission sources and secondary production. The dominant primary sources are traffic (11-15% of organic mass), biomass burning (13-15%) and cooking (up to 35% during meal hours). Secondary organic aerosol contributes more than 50% to the total organic mass and includes a highly oxidized factor from indeterminate and/or diverse sources and a less oxidized factor related to wood burning emissions. Black carbon was apportioned to traffic and wood burning sources using a model based on wavelength-dependent light absorption of these two combustion sources. The time series of organic and black carbon factors from related sources were strongly correlated. The similarities in aerosol composition, total mass and temporal variation between the three sites suggest that particulate pollution in Paris is dominated by regional factors, and that the emissions from Paris itself have a relatively low impact on its surroundings.

  7. Mass Measurements of Saharan Dust Aerosols in Puerto Rico

    NASA Astrophysics Data System (ADS)

    Armstrong, R. A.; Jimenez, B.; Detres, Y.

    2003-12-01

    During the summer months, Saharan dust aerosols reach maximum values throughout the Caribbean Region. The respirable fraction of this dust, measured as PM 2.5, has the potential to induce regional health impacts, such as asthma and allergic reactions in sensitive individuals. Surface measurements of dust aerosols were obtained at Fajardo, on the northeastern corner of Puerto Rico, since November 2000. The PM 2.5 and PM 10 size fractions from the filter samples were related to satellite and sunphotometer measurements of aerosol optical depth before, during, and after Saharan dust events. In 2002, PM 2.5 ranged from 2.5 to 18.4 ug/m-3 while PM 10 ranged from 11 to 60 ug/m-3. The PM 2.5 fraction was approximately 25% of the PM 10. Saharan dust aerosols are also responsible for substantial heavy metal deposition in the tropical western Atlantic. In 2001, Iron increase from less than 4 mg/g during the first four months of the year, to a maximum of 24 mg/g in June, with relatively high values from May through September. An AVHRR 4-year climatology of aerosol optical depth for northeastern Puerto Rico shows a well-defined maximum peak during the last week of June and first week of July.

  8. On the fractional solubility of copper in marine aerosols: Toxicity of aeolian copper revisited

    NASA Astrophysics Data System (ADS)

    Sholkovitz, Edward R.; Sedwick, Peter N.; Church, Thomas M.

    2010-10-01

    Paytan et al. (2009) argue that the atmospheric deposition of aerosols lead to copper concentrations that are potentially toxic to marine phytoplankton in a large area of tropical and subtropical North Atlantic Ocean. A key assumption in their model is that all marine aerosols (mineral dust and anthropogenic particles) have a high (40%) fractional solubility of copper. Our data show that the fractional solubility of copper for Saharan dust over the Sargasso Sea and Bermuda is significantly lower (1-7%). In contrast, anthropogenic aerosols with non-Saharan sources have significantly higher values (10-100%). Hence, the potential Cu toxicity in the tropical and subtropical North Atlantic should be re-estimated, given the low fractional solubility of Cu in the Saharan dust that dominates aerosol deposition to this region.

  9. Aerosol Analysis via Electrostatic Precipitation-Electrospray Ionization Mass Spectrometry.

    PubMed

    He, Siqin; Li, Lin; Duan, Hongxu; Naqwi, Amir; Hogan, Christopher J

    2015-07-01

    Electrospray ionization (ESI) is the preferred mode of ion generation for mass analysis of many organic species, as alternative ionization techniques can lead to appreciable analyte fragmentation. For this reason, ESI is an ideal method for the analysis of species within aerosol particles. However, because of their low concentrations (∼10 μg/m(3)) in most environments, ESI has been applied sparingly in aerosol particle analysis; aerosol mass spectrometers typically employ analyte volatilization followed by electron ionization or chemical ionization, which can lead to a considerable degree of analyte fragmentation. Here, we describe an approach to apply ESI to submicrometer and nanometer scale aerosol particles, which utilizes unipolar ionization to charge particles, electrostatic precipitation to collect particles on the tip of a Tungsten rod, and subsequently, by flowing liquid over the rod, ESI and mass analysis of the species composing collected particles. This technique, which we term electrostatic precipitation-ESI-MS (EP-ESI-MS), is shown to enable analysis of nanogram quantities of collected particles (from aerosol phase concentrations as low as 10(2) ng m(-3)) composed of cesium iodide, levoglucosan, and levoglucosan within a carbon nanoparticle matrix. With EP-ESI-MS, the integrated mass spectrometric signals are found to be a monotonic function of the mass concentration of analyte in the aerosol phase. We additionally show that EP-ESI-MS has a dynamic range of close to 5 orders of magnitude in mass, making it suitable for molecular analysis of aerosol particles in laboratory settings with upstream particle size classification, as well as analysis of PM 2.5 particles in ambient air. PMID:26024017

  10. Characterization of urban aerosol using aerosol mass spectrometry and proton nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Cleveland, M. J.; Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Lefer, B.; Rappenglück, B.

    2012-07-01

    Particulate matter was measured during August and September of 2006 in Houston as part of the Texas Air Quality Study II Radical and Aerosol Measurement Project. Aerosol size and composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Aerosol was dominated by sulfate (4.1 ± 2.6 μg m-3) and organic material (5.5 ± 4.0 μg m-3), with contributions of organic material from both primary (˜32%) and secondary (˜68%) sources. Secondary organic aerosol appears to be formed locally. In addition, 29 aerosol filter samples were analyzed using proton nuclear magnetic resonance (1H NMR) spectroscopy to determine relative concentrations of organic functional groups. Houston aerosols are less oxidized than those observed elsewhere, with smaller relative contributions of carbon-oxygen double bonds. These particles do not fit 1H NMR source apportionment fingerprints for identification of secondary, marine, and biomass burning organic aerosol, suggesting that a new fingerprint for highly urbanized and industrially influenced locations be established.

  11. Ambient aerosol analysis using aerosol-time-of-flight mass spectrometry

    SciTech Connect

    Prather, K.A.; Noble, C.A.; Liu, D.Y.; Silva, P.J.; Fergenson, D.F.

    1996-10-01

    We have recently developed a technique, Aerosol-Time-of-Flight Mass Spectrometry (ATOFMS), which is capable of real-time determination of the aerodynamic size and chemical composition of individual aerosol particles. In order to obtain such information, the techniques of aerodynamic particle sizing and time-of-flight mass spectrometry are combined in a single instrument. ATOFMS is being used for the direct analysis of ambient aerosols with the goal of establishing correlations between particle size and chemical composition. Currently, measurements are being made to establish potential links between the presence of particular types of particles with such factors as the time of day, weather conditions, and concentration levels of gaseous smog components such as NO{sub x} and ozone. This data will be used to help establish a better understanding of tropospheric gas-aerosol processes. This talk will discuss the operating principles of ATOFMS as well as present the results of ambient analysis studies performed in our laboratory.

  12. Urban increments of gaseous and aerosol pollutants and their sources using mobile aerosol mass spectrometry measurements

    NASA Astrophysics Data System (ADS)

    Elser, Miriam; Bozzetti, Carlo; El-Haddad, Imad; Maasikmets, Marek; Teinemaa, Erik; Richter, Rene; Wolf, Robert; Slowik, Jay G.; Baltensperger, Urs; Prévôt, André S. H.

    2016-06-01

    Air pollution is one of the main environmental concerns in urban areas, where anthropogenic emissions strongly affect air quality. This work presents the first spatially resolved detailed characterization of PM2.5 (particulate matter with aerodynamic equivalent diameter daero ≤ 2.5 µm) in two major Estonian cities, Tallinn and Tartu. The measurements were performed in March 2014 using a mobile platform. In both cities, the non-refractory (NR)-PM2.5 was characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) using a recently developed lens which increases the transmission of super-micron particles. Equivalent black carbon (eBC) and several trace gases including carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) were also measured. The chemical composition of PM2.5 was found to be very similar in the two cities. Organic aerosol (OA) constituted the largest fraction, explaining on average about 52 to 60 % of the PM2.5 mass. Four sources of OA were identified using positive matrix factorization (PMF): hydrocarbon-like OA (HOA, from traffic emissions), biomass burning OA (BBOA, from biomass combustion), residential influenced OA (RIOA, probably mostly from cooking processes with possible contributions from waste and coal burning), and oxygenated OA (OOA, related to secondary aerosol formation). OOA was the major OA source during nighttime, explaining on average half of the OA mass, while during daytime mobile measurements the OA was affected by point sources and dominated by the primary fraction. A strong increase in the secondary organic and inorganic components was observed during periods with transport of air masses from northern Germany, while the primary local emissions accumulated during periods with temperature inversions. Mobile measurements offered the identification of different source regions within the urban areas and the assessment of the extent to which pollutants concentrations exceeded regional background

  13. Investigating Types and Sources of Organic Aerosol in Rocky Mountain National Park Using Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L.

    2011-12-01

    The Rocky Mountain Atmospheric Nitrogen and Sulfur Study (RoMANS) focuses on identifying pathways and sources of nitrogen deposition in Rocky Mountain National Park (RMNP). Past work has combined measurements from a range of instrumentation such as annular denuders, PILS-IC, Hi-Vol samplers, and trace gas analyzers. Limited information from early RoMANS campaigns is available regarding organic aerosol. While prior measurements have produced a measure of total organic carbon mass, high time resolution measures of organic aerosol concentration and speciation are lacking. One area of particular interest is characterizing the types, sources, and amounts of organic nitrogen aerosol. Organic nitrogen measurements in RMNP wet deposition reveal a substantial contribution to the total reactive nitrogen deposition budget. In this study an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in summer 2010 at RMNP to investigate organic aerosol composition and its temporal variability. The species timeline and diurnal species variations are combined with meteorological data to investigate local transport events and chemistry; transport from the Colorado Front Range urban corridor appears to be more significant for inorganic species than for the overall organic aerosol mass. Considerable variation in organic aerosol concentration is observed (0.5 to 20 μg/m3), with high concentration episodes lasting between hours and two days. High resolution AMS data are analyzed for organic aerosol, including organic nitrogen species that might be expected from local biogenic emissions, agricultural activities, and secondary reaction products of combustion emissions. Positive matrix factorization reveals that semi-volatile oxidized OA, low-volatility oxidized OA, and biomass burning OA comprise most organic mass; the diurnal profile of biomass burning OA peaks at four and nine pm and may arise from local camp fires, while constant concentrations of

  14. Characterization of near-highway submicron aerosols in New York City with a high-resolution aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Sun, Y. L.; Zhang, Q.; Schwab, J. J.; Chen, W.-N.; Bae, M.-S.; Hung, H.-M.; Lin, Y.-C.; Ng, N. L.; Jayne, J.; Massoli, P.; Williams, L. R.; Demerjian, K. L.

    2012-02-01

    Knowledge of the variations of mass concentration, chemical composition and size distributions of submicron aerosols near roadways is of importance for reducing exposure assessment uncertainties in health effects studies. The goal of this study is to deploy and evaluate an Atmospheric Sciences Research Center-Mobile Laboratory (ASRC-ML), equipped with a suite of rapid response instruments for characterization of traffic plumes, adjacent to the Long Island Expressway (LIE) - a high-traffic highway in the New York City Metropolitan Area. In total, four measurement periods, two in the morning and two in the evening were conducted at a location approximately 30 m south of the LIE. The mass concentrations and size distributions of non-refractory submicron aerosol (NR-PM1) species were measured in situ at a time resolution of 1 min by an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer, along with rapid measurements (down to 1 Hz) of gaseous pollutants (e.g. HCHO, NO2, NO, O3, and CO2, etc.), black carbon (BC), and particle number concentrations and size distributions. Particulate organics varied dramatically during periods with high traffic influences from the nearby roadway. The variations were mainly observed in the hydrocarbon-like organic aerosol (HOA), a surrogate for primary OA from vehicle emissions. The inorganic species (sulfate, ammonium, and nitrate) and oxygenated OA (OOA) showed much smoother variations indicating minor impacts from traffic emissions. The concentration and chemical composition of NR-PM1 also varied differently on different days depending on meteorology, traffic intensity and vehicle types. Overall, organics dominated the traffic-related NR-PM1 composition (>60%) with HOA accounting for a major fraction of OA. The traffic-influenced organics showed two distinct modes in mass-weighted size distributions, peaking at ∼120 nm and 500 nm (vacuum aerodynamic diameter, Dva), respectively. OOA and inorganic species appear to be

  15. Studies of Ambient and Chamber Aerosol Composition using the Aerosol Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Craven, Jill Suzanne

    This thesis presents composition measurements for atmospherically relevant inorganic and organic aerosol from laboratory and ambient measurements using the Aerodyne aerosol mass spectrometer. Studies include the oxidation of dodecane in the Caltech environmental chambers, and several aircraft- and ground-based field studies, which include the quantification of wildfire emissions off the coast of California, and Los Angeles urban emissions. The oxidation of dodecane by OH under low NO conditions and the formation of secondary organic aerosol (SOA) was explored using a gas-phase chemical model, gas-phase CIMS measurements, and high molecular weight ion traces from particlephase HR-TOF-AMS mass spectra. The combination of these measurements support the hypothesis that particle-phase chemistry leading to peroxyhemiacetal formation is important. Positive matrix factorization (PMF) was applied to the AMS mass spectra which revealed three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition. Airborne measurements of biomass burning emissions from a chaparral fire on the central Californian coast were carried out in November 2009. Physical and chemical changes were reported for smoke ages 0--4 h old. CO 2 normalized ammonium, nitrate, and sulfate increased, whereas the normalized OA decreased sharply in the first 1.5--2 h, and then slowly increased for the remaining 2 h (net decrease in normalized OA). Comparison to wildfire samples from the Yucatan revealed that factors such as relative humidity, incident UV radiation, age of smoke, and concentration of emissions are important for wildfire evolution. Ground-based aerosol composition is reported for Pasadena, CA during the sumix mer of 2009. The OA component, which dominated the submicron aerosol mass, was deconvolved into hydrocarbon-like organic aerosol (HOA), semi-volatile oxidized organic aerosol (SVOOA), and low-volatility oxidized organic aerosol

  16. Development of a continuous aerosol mass concentration measurement device.

    PubMed

    Bémer, D; Thomas, D; Contal, P; Subra, I

    2003-08-01

    A dynamic aerosol mass concentration measurement device has been developed for personal sampling. Its principle consists in sampling the aerosol on a filter and monitoring the change of pressure drop over time (Delta P). Ensuring that the linearity of the Delta P = f(mass of particles per unit area of filter) relationship has been well established, the change of concentration can be deduced. The response of the system was validated in the laboratory with a 3.5 microm alumina aerosol (mass median diameter) generated inside a 1-m(3) ventilated enclosure. As the theory predicted that the mass sensitivity of the system would vary inversely with the square of the particle diameter, only sufficiently fine aerosols were able to be measured. The system was tested in the field in a mechanical workshop in the vicinity of an arc-welding station. The aerosol produced by welding is indeed particularly well-adapted due to the sub-micronic size of the particles. The device developed, despite this limitation, has numerous advantages over other techniques: robustness, compactness, reliability of calibration, and ease of use.

  17. OMI tropospheric NO2 air mass factors over South America: effects of biomass burning aerosols

    NASA Astrophysics Data System (ADS)

    Castellanos, P.; Boersma, K. F.; Torres, O.; de Haan, J. F.

    2015-09-01

    Biomass burning is an important and uncertain source of aerosols and NOx (NO + NO2) to the atmosphere. Satellite observations of tropospheric NO2 are essential for characterizing this emissions source, but inaccuracies in the retrieval of NO2 tropospheric columns due to the radiative effects of aerosols, especially light-absorbing carbonaceous aerosols, are not well understood. It has been shown that the O2-O2 effective cloud fraction and pressure retrieval is sensitive to aerosol optical and physical properties, including aerosol optical depth (AOD). Aerosols implicitly influence the tropospheric air mass factor (AMF) calculations used in the NO2 retrieval through the effective cloud parameters used in the independent pixel approximation. In this work, we explicitly account for the effects of biomass burning aerosols in the Ozone Monitoring Instrument (OMI) tropospheric NO2 AMF calculation for cloud-free scenes. We do so by including collocated aerosol extinction vertical profile observations from the CALIOP instrument, and aerosol optical depth (AOD) and single scattering albedo (SSA) retrieved by the OMI near-UV aerosol algorithm (OMAERUV) in the DISAMAR radiative transfer model. Tropospheric AMFs calculated with DISAMAR were benchmarked against AMFs reported in the Dutch OMI NO2 (DOMINO) retrieval; the mean and standard deviation of the difference was 0.6 ± 8 %. Averaged over three successive South American biomass burning seasons (2006-2008), the spatial correlation in the 500 nm AOD retrieved by OMI and the 532 nm AOD retrieved by CALIOP was 0.6, and 68 % of the daily OMAERUV AOD observations were within 30 % of the CALIOP observations. Overall, tropospheric AMFs calculated with observed aerosol parameters were on average 10 % higher than AMFs calculated with effective cloud parameters. For effective cloud radiance fractions less than 30 %, or effective cloud pressures greater than 800 hPa, the difference between tropospheric AMFs based on implicit and

  18. Aerosol detection efficiency in inductively coupled plasma mass spectrometry

    DOE PAGES

    Hubbard, Joshua A.; Zigmond, Joseph A.

    2016-03-02

    We used an electrostatic size classification technique to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Moreover, we counted size-segregated particles with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized bymore » the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10-5 to 10-11. Free molecular heat and mass transfer theory was

  19. Aerosol detection efficiency in inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hubbard, Joshua A.; Zigmond, Joseph A.

    2016-05-01

    An electrostatic size classification technique was used to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Size-segregated particles were counted with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized by the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10- 5 to 10- 11. Free molecular heat and mass transfer theory was applied, but

  20. Aerosol propellant interference with clinical mass spectrometers.

    PubMed

    Kharasch, E D; Sivarajan, M

    1991-04-01

    Metered dose inhalers containing halogenated propellants may interfere with mass spectrometer quantitation of halogenated inhalation anesthetics. We identify the propellant(s) in a commercially available metered dose inhaler that caused erroneous mass spectrometer readings. In addition, we identify the causes of different types of interference in different mass spectrometers. PMID:2072131

  1. Measuring Bipolar Charge and Mass Distributions of Powder Aerosols by a Novel Tool (BOLAR).

    PubMed

    Wong, Jennifer; Lin, Yu-Wei; Kwok, Philip Chi Lip; Niemelä, Ville; Crapper, John; Chan, Hak-Kim

    2015-09-01

    The Bipolar Charge Analyzer (BOLAR) was evaluated for measuring bipolar electrostatic charge and mass distributions of powder aerosols generated from a dry powder inhaler. Mannitol powder (5, 10, and 20 mg) was dispersed using an Osmohaler inhaler into the BOLAR at air flow rates of 30 or 60 L/min. As the aerosol sample was drawn through the BOLAR, the air flow was divided into six equal fractions. Five of them entered individual detection tubes with a defined cutoff diameter in the range of 0.95 to 16.36 μm (depending on the flow rate) and the remaining (i.e., the sixth) fraction passed through a reference chamber. The aerosols that entered the detection tubes were separated according to the particle charge polarity (positive, negative, or neutral) and charge was measured by separate electrometers. The deposited powder of a single actuation from the inhaler was chemically assayed using high performance liquid chromatography. Additionally, the aerosol measurements were conducted on a modified Classic Electrical Low Pressure Impactor (ELPI) for comparison of the net specific charge per size fraction. Spray-dried mannitol carried significantly different positively and negatively charged particles in each of the five defined particle size fractions. The charge-to-mass ratio (q/m) of positively charged particles ranged from +1.11 to +32.57 pC/μg and negatively charged particles ranged from -1.39 to -9.25 pC/μg, resulting in a net q/m of -3.08 to +13.34 pC/μg. The net q/m values obtained on the modified ELPI ranged from -5.18 to +4.81 pC/μg, which were comparable to the BOLAR measurements. This is the first full report to utilize the BOLAR to measure bipolar charge and mass distributions of a powder aerosol. Positively and negatively charged particles were observed within each size fraction, and their corresponding q/m profiles were successfully characterized. Despite some potential drawbacks, the BOLAR has provided a new platform for investigating bipolar charge

  2. The on-line analysis of aerosol-delivered pharmaceuticals via single particle aerosol mass spectrometry.

    PubMed

    Morrical, Bradley D; Balaxi, Maria; Fergenson, David

    2015-07-15

    The use of single particle aerosol mass spectrometry (SPAMS) was evaluated for the analysis of inhaled pharmaceuticals to determine the mass distribution of the individual active pharmaceutical ingredients (API) in both single ingredient and combination drug products. SPAMS is an analytical technique where the individual aerodynamic diameters and chemical compositions of many aerosol particles are determined in real-time. The analysis was performed using a Livermore Instruments SPAMS 3.0, which allowed the efficient analysis of aerosol particles with broad size distributions and can acquire data even under a very large particle load. Data similar to what would normally require roughly three days of experimentation and analysis was collected in a five minute period and analyzed automatically. The results were computed to be comparable to those returned by a typical Next Generation Impactor (NGI) particle size distribution experiment.

  3. Characterization of ambient aerosols at the San Francisco International Airport using BioAerosol Mass Spectrometry

    SciTech Connect

    Steele, P T; McJimpsey, E L; Coffee, K R; Fergenson, D P; Riot, V J; Tobias, H J; Woods, B W; Gard, E E; Frank, M

    2006-03-16

    The BioAerosol Mass Spectrometry (BAMS) system is a rapidly fieldable, fully autonomous instrument that can perform correlated measurements of multiple orthogonal properties of individual aerosol particles. The BAMS front end uses optical techniques to nondestructively measure a particle's aerodynamic diameter and fluorescence properties. Fluorescence can be excited at 266nm or 355nm and is detected in two broad wavelength bands. Individual particles with appropriate size and fluorescence properties can then be analyzed more thoroughly in a dual-polarity time-of-flight mass spectrometer. Over the course of two deployments to the San Francisco International Airport, more than 6.5 million individual aerosol particles were fully analyzed by the system. Analysis of the resulting data has provided a number of important insights relevant to rapid bioaerosol detection, which are described here.

  4. MASS SPECTROMETRY OF INDIVIDUAL AEROSOL PARTICLES. (R823980)

    EPA Science Inventory

    Typically, in real-time aerosol mass spectrometry (RTAMS), individual airborne particles
    are ablated and ionized with a single focused laser pulse. This technique yields information that
    permits bulk characterization of the particle, but information about the particle's sur...

  5. THE MASS ACCOMMODATION COEFFICIENT OF AMMONIUM NITRATE AEROSOL. (R823514)

    EPA Science Inventory

    The mass transfer rate of pure ammonium nitrate between the aerosol and gas phases was
    quantified experimentally by the use of the tandem differential mobility analyzer/scanning mobility
    particle sizer (TDMA/SMPS) technique. Ammonium nitrate particles 80-220 nm in diameter<...

  6. Aerosol mass spectrometry systems and methods

    DOEpatents

    Fergenson, David P.; Gard, Eric E.

    2013-08-20

    A system according to one embodiment includes a particle accelerator that directs a succession of polydisperse aerosol particles along a predetermined particle path; multiple tracking lasers for generating beams of light across the particle path; an optical detector positioned adjacent the particle path for detecting impingement of the beams of light on individual particles; a desorption laser for generating a beam of desorbing light across the particle path about coaxial with a beam of light produced by one of the tracking lasers; and a controller, responsive to detection of a signal produced by the optical detector, that controls the desorption laser to generate the beam of desorbing light. Additional systems and methods are also disclosed.

  7. The Hohenpeissenberg aerosol characterization experiment (HAZE2002): Aerosol composition derived from mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hock, N.; Berresheim, H.; Borrmann, S.; Poeschl, U.; Roempp, A.; Schneider, J.

    2003-04-01

    The HAZE Experiment was conducted between 17.05.2002 and 31.05.2002, at the meteorological observatory of the Deutsche Wetterdienst (DWD) at Hohenpeissenberg (47^o48'N,11^o02'E, 985m). The objective was to make essential progress in understanding of the physical and chemical properties of the atmospheric aerosol, in particular relating to the Gas-To-Particle-Conversion and the interaction with meteorological processes. The measurements included online mass spectrometric analysis using the Aerosol Mass Spectrometer (AMS), filter samples with GC analyses of organic compounds, particle size distribution (Electrical Low Pressure Impactor (ELPI), SMPS, OPC), as well as the total particle concentration (CPC). Additionally, several gas-phase substances were measured (e.g. Benzene, Acetone). The measurements obtained with the AMS show a strong variability of the aerosol composition. The non-refractory aerosol composition was dominated by nitrate, sulphate, and organics, whereas ammonium was surprisingly low. High number concentration of up to 14000 particles/cm^3 were observed. These particles mostly had diameters between 200 nm and 400 nm and were mainly composed of ammonium sulphate and ammonium nitrate. Various meteorological conditions allowed to study their influence on the aerosol. For example, on rainy days the concentrations of ammonium sulphate particles decreased, whereas the concentrations of ammonium nitrate particles increased.

  8. Significant contributions of fungal spores to the organic carbon and to the aerosol mass balance of the urban atmospheric aerosol

    NASA Astrophysics Data System (ADS)

    Bauer, Heidi; Schueller, Elisabeth; Weinke, Gert; Berger, Anna; Hitzenberger, Regina; Marr, Iain L.; Puxbaum, Hans

    Fungal spores are ubiquitous components of atmospheric aerosols and are therefore also contributors to the organic carbon (OC) component and to the mass of PM 10 (PM—particulate matter) aerosols. In this study we use spore counts and an experimentally derived factor of 13 pg C and of 33 pg fresh weight per spore for assessing quantitatively the contribution to OC and PM 10. The concentrations of airborne fungal spores were determined at a suburban (Schafberg) and a traffic-dominated urban site (Rinnböckstrasse) in Vienna, Austria, during spring and summer. Fungal spores OC ranged from 22 to 677 ng m -3 with a summer mean value of around 350 ng m -3 at the suburban site and 300 ng m -3 at the urban traffic site. At the suburban site fungal spores contributed on average 6% in spring and 14% in summer to aerosol OC mass concentration. At the traffic-dominated site fungal spores accounted for 2% of OC in spring and for 8% in summer. The fungal contribution to PM 10 was also notable and amounted to 3% and 7% at the suburban and to 1% and 4% at the urban site in spring and summer, respectively. Impactor measurements of OC at the suburban site showed that in summer fungal spores were predominant contributors to the coarse aerosol OC, and accounted on average for 60% of the OC in the PM 2-10 fraction. Fungal spores thus can be regarded as main components to PM 10, total OC and, most importantly, coarse OC even in urban areas.

  9. Mass spectra deconvolution of low, medium, and high volatility biogenic secondary organic aerosol.

    PubMed

    Kostenidou, Evangelia; Lee, Byong-Hyoek; Engelhart, Gabriella J; Pierce, Jeffrey R; Pandis, Spyros N

    2009-07-01

    Secondary organic aerosol (SOA) consists of compounds with a wide range of volatilities and its ambient concentration is sensitive to this volatility distribution. Recent field studies have shown that the typical mass spectrum of ambient oxygenated organic aerosol (OOA) as measured by the Aerodyne Aerosol Mass Spectrometer (AMS) is quite different from the SOA mass spectra reported in smog chamber experiments. Part of this discrepancy is due to the dependence of SOA composition on the organic aerosol concentration. High precursor concentrations lead to higher concentrations of the more volatile species in the produced SOA while at lower concentrations the less volatile compounds dominate the SOA composition. alpha-Pinene, beta-pinene, d-limonene, and beta-caryophyllene ozonolysis experiments were performed at moderate concentration levels. Using a thermodenuder the more volatile SOA species were removed achieving even lower SOA concentration. The less volatile fraction was then chemically characterized by an AMS. The signal fraction of m/z44, and thus the concentration of C02+, is significantly higher for the less volatile SOA. High NO(x) conditions result in less oxidized SOA than low NO(x) conditions, while increasing relative humidity levels results in more oxidized products for limonene but has little effect on alpha-and beta-pinene SOA. Combining a smog chamber with a thermodenuder model employing the volatility basis-set framework, the AMS SOA mass spectrum for each experiment and for each precursor is deconvoluted into low, medium, and high volatility component mass spectra. The spectrum of the surrogate component with the lower volatility is quite similar to that of ambient OOA.

  10. Molecular Characterization of Nitrogen Containing Organic Compounds in Biomass Burning Aerosols Using High Resolution Mass Spectrometry

    SciTech Connect

    Laskin, Alexander; Smith, Jeffrey S.; Laskin, Julia

    2009-05-13

    Although nitrogen-containing organic compounds (NOC) are important components of atmospheric aerosols, little is known about their chemical compositions. Here we present detailed characterization of the NOC constituents of biomass burning aerosol (BBA) samples using high resolution electrospray ionization mass spectrometry (ESI/MS). Accurate mass measurements combined with MS/MS fragmentation experiments of selected ions were used to assign molecular structures to individual NOC species. Our results indicate that N-heterocyclic alkaloid compounds - species naturally produced by plants and living organisms - comprise a substantial fraction of NOC in BBA samples collected from test burns of five biomass fuels. High abundance of alkaloids in test burns of ponderosa pine - a widespread tree in the western U.S. areas frequently affected by large scale fires - suggests that N-heterocyclic alkaloids in BBA can play a significant role in dry and wet deposition of fixed nitrogen in this region.

  11. Mass spectroscopy of single aerosols from field measurements

    SciTech Connect

    Thomson, D.S.; Murphy, D.M.

    1995-12-31

    We are developing an aircraft instrument for the chemical analysis of individual ambient aerosols in real time. In order to test the laboratory version of this instrument, we participated in a field campaign near the continental divide in Colorado in September, 1993. During this campaign, over 5000 mass spectra of ambient aerosols were collected. Analysis of the negative ion spectra shows that sulfate was the most commonly seen component of smaller particles, while nitrate was more common in larger particles. Organic compounds are present in most particles, and we believe we can distinguish inorganic carbon in some particles. Although numerous distinct classes of particles were observed, indicating external mixtures, almost all of these particle types were themselves mixtures of several compounds. Finally, we note that although the field site experienced distinct polluted and unpolluted episodes, aerosol composition did not correlate with gas phase chemistry.

  12. Derivation of Aerosol Columnar Mass from MODIS Optical Depth

    NASA Technical Reports Server (NTRS)

    Gasso, Santiago; Hegg, Dean A.

    2003-01-01

    In order to verify performance, aerosol transport models (ATM) compare aerosol columnar mass (ACM) with those derived from satellite measurements. The comparison is inherently indirect since satellites derive optical depths and they use a proportionality constant to derive the ACM. Analogously, ATMs output a four dimensional ACM distribution and the optical depth is linearly derived. In both cases, the proportionality constant requires a direct intervention of the user by prescribing the aerosol composition and size distribution. This study introduces a method that minimizes the direct user intervention by making use of the new aerosol products of MODIS. A parameterization is introduced for the derivation of columnar aerosol mass (AMC) and CCN concentration (CCNC) and comparisons between sunphotometer, MODIS Airborne Simulator (MAS) and in-measurements are shown. The method still relies on the scaling between AMC and optical depth but the proportionality constant is dependent on the MODIS derived r$_{eff}$,\\eta (contribution of the accumulation mode radiance to the total radiance), ambient RH and an assumed constant aerosol composition. The CCNC is derived fkom a recent parameterization of CCNC as a function of the retrieved aerosol volume. By comparing with in-situ data (ACE-2 and TARFOX campaigns), it is shown that retrievals in dry ambient conditions (dust) are improved when using a proportionality constant dependent on r$ {eff}$ and \\eta derived in the same pixel. In high humidity environments, the improvement inthe new method is inconclusive because of the difficulty in accounting for the uneven vertical distribution of relative humidity. Additionally, two detailed comparisons of AMC and CCNC retrieved by the MAS algorithm and the new method are shown. The new method and MAS retrievals of AMC are within the same order of magnitude with respect to the in-situ measurements of aerosol mass. However, the proposed method is closer to the in-situ measurements than

  13. Organic aerosol mixing observed by single-particle mass spectrometry.

    PubMed

    Robinson, Ellis Shipley; Saleh, Rawad; Donahue, Neil M

    2013-12-27

    We present direct measurements of mixing between separately prepared organic aerosol populations in a smog chamber using single-particle mass spectra from the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Docosane and docosane-d46 (22 carbon linear solid alkane) did not show any signs of mixing, but squalane and squalane-d62 (30 carbon branched liquid alkane) mixed on the time scale expected from a condensational-mixing model. Docosane and docosane-d46 were driven to mix when the chamber temperature was elevated above the melting point for docosane. Docosane vapors were shown to mix into squalane-d62, but not the other way around. These results are consistent with low diffusivity in the solid phase of docosane particles. We performed mixing experiments on secondary organic aerosol (SOA) surrogate systems finding that SOA derived from toluene-d8 (a surrogate for anthropogenic SOA (aSOA)) does not mix into squalane (a surrogate for hydrophobic primary organic aerosol (POA)) but does mix into SOA derived from α-pinene (biogenic SOA (bSOA) surrogate). For the aSOA/POA, the volatility of either aerosol does not limit gas-phase diffusion, indicating that the two particle populations do not mix simply because they are immiscible. In the aSOA/bSOA system, the presence of toluene-d8-derived SOA molecules in the α-pinene-derived SOA provides evidence that the diffusion coefficient in α-pinene-derived SOA is high enough for mixing on the time scale of 1 min. The observations from all of these mixing experiments are generally invisible to bulk aerosol composition measurements but are made possible with single-particle composition data.

  14. Reactions and mass spectra of complex particles using Aerosol CIMS

    NASA Astrophysics Data System (ADS)

    Hearn, John D.; Smith, Geoffrey D.

    2006-12-01

    Aerosol chemical ionization mass spectrometry (CIMS) is used both on- and off-line for the analysis of complex laboratory-generated and ambient particles. One of the primary advantages of Aerosol CIMS is the low degree of ion fragmentation, making this technique well suited for investigating the reactivity of complex particles. To demonstrate the usefulness of this "soft" ionization, particles generated from meat cooking were reacted with ozone and the composition was monitored as a function of reaction time. Two distinct kinetic regimes were observed with most of the oleic acid in these particles reacting quickly but with 30% appearing to be trapped in the complex mixture. Additionally, detection limits are measured to be sufficiently low (100-200 ng/m3) to detect some of the more abundant constituents in ambient particles, including sulfate, which is measured in real-time at 1.2 [mu]g/m3. To better characterize complex aerosols from a variety of sources, a novel off-line collection method was also developed in which non-volatile and semi-volatile organics are desorbed from particles and concentrated in a cold U-tube. Desorption from the U-tube followed by analysis with Aerosol CIMS revealed significant amounts of nicotine in cigarette smoke and levoglucosan in oak and pine smoke, suggesting that this may be a useful technique for monitoring particle tracer species. Additionally, secondary organic aerosol formed from the reaction of ozone with R-limonene and volatile organics from orange peel were analyzed off-line showing large molecular weight products (m/z > 300 amu) that may indicate the formation of oligomers. Finally, mass spectra of ambient aerosol collected offline reveal a complex mixture of what appears to be highly processed organics, some of which may contain nitrogen.

  15. Direct gravimetric determination of aerosol mass concentration in central antarctica.

    PubMed

    Annibaldi, Anna; Truzzi, Cristina; Illuminati, Silvia; Scarponi, Giuseppe

    2011-01-01

    In Antarctica, experimental difficulties due to extreme conditions have meant that aerosol mass has rarely been measured directly by gravimetry, and only in coastal areas where concentrations were in the range of 1-7 μg m(-3). The present work reports on a careful differential weighing methodology carried out for the first time on the plateau of central Antarctica (Dome C, East Antarctica). To solve problems of accurate aerosol mass measurements, a climatic room was used for conditioning and weighing filters. Measurements were carried out in long stages of several hours of readings with automatic recording of temperature/humidity and mass. This experimental scheme allowed us to sample from all the measurements (up to 2000) carried out before and after exposure, those which were recorded under the most stable humidity conditions and, even more importantly, as close to each other as possible. The automatic reading of the mass allowed us in any case to obtain hundreds of measurements from which to calculate average values with uncertainties sufficiently low to meet the requirements of the differential weighing procedure (±0.2 mg in filter weighing, between ±7% and ±16% both in aerosol mass and concentration measurements). The results show that the average summer aerosol mass concentration (aerodynamic size ≤10 μm) in central Antarctica is about 0.1 μg m(-3), i.e., about 1/10 of that of coastal Antarctic areas. The concentration increases by about 4-5 times at a site very close to the station.

  16. Direct gravimetric determination of aerosol mass concentration in central antarctica.

    PubMed

    Annibaldi, Anna; Truzzi, Cristina; Illuminati, Silvia; Scarponi, Giuseppe

    2011-01-01

    In Antarctica, experimental difficulties due to extreme conditions have meant that aerosol mass has rarely been measured directly by gravimetry, and only in coastal areas where concentrations were in the range of 1-7 μg m(-3). The present work reports on a careful differential weighing methodology carried out for the first time on the plateau of central Antarctica (Dome C, East Antarctica). To solve problems of accurate aerosol mass measurements, a climatic room was used for conditioning and weighing filters. Measurements were carried out in long stages of several hours of readings with automatic recording of temperature/humidity and mass. This experimental scheme allowed us to sample from all the measurements (up to 2000) carried out before and after exposure, those which were recorded under the most stable humidity conditions and, even more importantly, as close to each other as possible. The automatic reading of the mass allowed us in any case to obtain hundreds of measurements from which to calculate average values with uncertainties sufficiently low to meet the requirements of the differential weighing procedure (±0.2 mg in filter weighing, between ±7% and ±16% both in aerosol mass and concentration measurements). The results show that the average summer aerosol mass concentration (aerodynamic size ≤10 μm) in central Antarctica is about 0.1 μg m(-3), i.e., about 1/10 of that of coastal Antarctic areas. The concentration increases by about 4-5 times at a site very close to the station. PMID:21141836

  17. A Physically Based Framework for Modelling the Organic Fractionation of Sea Spray Aerosol from Bubble Film Langmuir Equilibria

    SciTech Connect

    Burrows, Susannah M.; Ogunro, O.; Frossard, Amanda; Russell, Lynn M.; Rasch, Philip J.; Elliott, S.

    2014-12-19

    The presence of a large fraction of organic matter in primary sea spray aerosol (SSA) can strongly affect its cloud condensation nuclei activity and interactions with marine clouds. Global climate models require new parameterizations of the SSA composition in order to improve the representation of these processes. Existing proposals for such a parameterization use remotely-sensed chlorophyll-a concentrations as a proxy for the biogenic contribution to the aerosol. However, both observations and theoretical considerations suggest that existing relationships with chlorophyll-a, derived from observations at only a few locations, may not be representative for all ocean regions. We introduce a novel framework for parameterizing the fractionation of marine organic matter into SSA based on a competitive Langmuir adsorption equilibrium at bubble surfaces. Marine organic matter is partitioned into classes with differing molecular weights, surface excesses, and Langmuir adsorption parameters. The classes include a lipid-like mixture associated with labile dissolved organic carbon (DOC), a polysaccharide-like mixture associated primarily with semi-labile DOC, a protein-like mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture. Box model calculations have been performed for several cases of organic adsorption to illustrate the underlying concepts. We then apply the framework to output from a global marine biogeochemistry model, by partitioning total dissolved organic carbon into several classes of macromolecule. Each class is represented by model compounds with physical and chemical properties based on existing laboratory data. This allows us to globally map the predicted organic mass fraction of the nascent submicron sea spray aerosol. Predicted relationships between chlorophyll-\\textit{a} and organic fraction are similar to existing empirical

  18. Relating Aerosol Mass and Optical Depth in the Summertime Continental Boundary Layer

    NASA Astrophysics Data System (ADS)

    Brock, C. A.; Wagner, N.; Middlebrook, A. M.; Attwood, A. R.; Washenfelder, R. A.; Brown, S. S.; McComiskey, A. C.; Gordon, T. D.; Welti, A.; Carlton, A. G.; Murphy, D. M.

    2014-12-01

    Aerosol optical depth (AOD), the column-integrated ambient aerosol light extinction, is determined from satellite and ground-based remote sensing measurements. AOD is the parameter most often used to validate earth system model simulations of aerosol mass. Relating aerosol mass to AOD, however, is problematic due to issues including aerosol water uptake as a function of relative humidity (RH) and the complicated relationship between aerosol physicochemical properties and light extinction. Measurements of aerosol microphysical, chemical, and optical properties help to constrain the relationship between aerosol mass and optical depth because aerosol extinction at ambient RH is a function of the abundance, composition and size distribution of the aerosol. We use vertical profiles of humidity and dry aerosol extinction observed in the southeastern United States (U.S.) to examine the relationship between submicron aerosol mass concentration and extinction at ambient RH. We show that the κ-Köhler parameterization directly, and without additional Mie calculations, describes the change in extinction with varying RH as a function of composition for both aged aerosols typical of the polluted summertime continental boundary layer and the biomass burning aerosols we encountered. We calculate how AOD and the direct radiative effect in the eastern U.S. have likely changed due to trends in aerosol composition in recent decades. We also examine the sensitivity of AOD to the RH profile and to aerosol composition, size distribution and abundance.

  19. Molecular composition of atmospheric aerosols from Halley Bay, Antarctica, using ultra-high resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Brough, Neil; Rincon, Angela; Jones, Anna; Kalberer, Markus

    2016-04-01

    Antarctica is one of the few pristine places to study natural processes of atmospheric aerosols and anthropogenic impacts on the clean remote atmosphere. Although stratospheric aerosol in Antarctica has now been explored in some detail because of the ozone depletion phenomenon, tropospheric aerosol particles in Antarctica remain very little studied. The main goal of this work is to identify in detail the organic chemical composition of aerosol from Halley Bay station, which is located on the Brunt Ice Shelf floating on the Weddell Sea in Antarctica. In this study we characterise the molecular composition of aerosols from three seasons (summer, autumn and winter in 2012) using ultra-high resolution mass spectrometry (UHRMS). The technique provides high accuracy and high mass resolving power that allows determining unambiguous number of organic compounds present in complex organic mixtures (Noziere et al., 2015). The molecular composition interpretation was facilitated using visualisation methods (e.g. double bond equivalent, Van Krevelen diagrams, Kendrick mass analysis, and carbon oxidation state), which allowed to identify patterns, such as differences between sampling times and atmospheric processes. The majority of the identified compounds were attributed to nitrogen and sulphur containing species which exhibited very strong seasonal trends. Relatively large fraction (up to 30% of the total number of molecules) of these species contained very low hydrogen to carbon ratios (below 1) indicating that the site is impacted by anthropogenic emissions. Influences of the meteorological parameters and air mass trajectories on the molecular composition are discussed. Nozière et al., The Molecular Identification of Organic Compounds in the Atmosphere: State of the Art and Challenges, Chem. Rev., 115, 3920-3983, 2015.

  20. Ambient aerosol analysis using aerosol-time-of-flight mass spectrometry

    SciTech Connect

    Prather, K.A.; Noble, C.; Salt, K.; Nordmeyer, T.; Fergenson, D.; Morrical, B.

    1995-12-31

    Particulate pollution is an area of growing concern in light of recent studies which suggest a link between high concentrations of ambient PM{sub 10} (particles with diameters equal to or less than 10 {mu}m) and adverse health effects ranging from respiratory ailments to premature death. However, analytical chemistry techniques aimed at sampling and analysis of atmospheric aerosols are extremely limited in comparison to the number of methods that exist for studying gas phase smog components. As a result, current government regulations for levels of ambient particulates are necessarily general, lacking any chemical specificity. The authors have recently developed a technique, Aerosol-Time-of-Flight Mass Spectrometry (ATOFMS), which is capable of real-time determination of the size and chemical composition of individual aerosol particles. In order to obtain such information, the techniques of aerodynamic particle sizing and time-of-flight spectrometry are combined in a single instrument. In one of the aerosol studies performed in this laboratory, this instrument is being used for the direct analysis of ambient aerosols with the goal of establishing correlations between particle size and chemical composition. To date, the authors have observed very distinct size/composition correlations for organic and inorganic particles.

  1. New characteristics of submicron aerosols and factor analysis of combined organic and inorganic aerosol mass spectra during winter in Beijing

    NASA Astrophysics Data System (ADS)

    Zhang, J. K.; Ji, D. S.; Liu, Z. R.; Hu, B.; Wang, L. L.; Huang, X. J.; Wang, Y. S.

    2015-07-01

    In recent years, an increasing amount of attention has been paid to heavy haze pollution in Beijing, China. In addition to Beijing's population of approximately 20 million and its 5 million vehicles, nearby cities and provinces are host to hundreds of heavily polluting industries. In this study, a comparison between observations in January 2013 and January 2014 showed that non-refractory PM1 (NR-PM1) pollution was weaker in January 2014, which was primarily caused by variations in meteorological conditions. For the first time, positive matrix factorization (PMF) was applied to the merged high-resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer measurements in Beijing, and the sources and evolution of NR-PM1 in January 2014 were investigated. The two factors, NO3-OA1 and NO3-OA2, were primarily composed of ammonium nitrate, and each showed a different degree of oxidation and diurnal variation. The organic fraction of SO4-OA showed the highest degree of oxidation of all PMF factors. The hydrocarbon-like organic aerosol (OA) and cooking OA factors contained negligible amounts of inorganic species. The coal combustion OA factor contained a high contribution from chloride in its mass spectrum. The NR-PM1 composition showed significant variations in January 2014, in which the contribution of nitrate clearly increased during heavy pollution events. The most effective way to control fine particle pollution in Beijing is through joint prevention and control measures at the regional level, rather than a focus on an individual city, especially for severe haze events.

  2. 40 CFR Table F-5 to Subpart F of... - Estimated Mass Concentration Measurement of PM2.5 for Idealized “Typical” Coarse Aerosol Size...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Estimated Mass Concentration... 53—Estimated Mass Concentration Measurement of PM2.5 for Idealized “Typical” Coarse Aerosol Size... Concentration (µg/m3) Estimated Mass Concentration Measurement (µg/m3) Ideal Sampler Fractional...

  3. 40 CFR Table F-5 to Subpart F of... - Estimated Mass Concentration Measurement of PM 2.5 for Idealized “Typical” Coarse Aerosol Size...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Estimated Mass Concentration... 53—Estimated Mass Concentration Measurement of PM 2.5 for Idealized “Typical” Coarse Aerosol Size... Concentration (µg/m3) Estimated Mass Concentration Measurement (µg/m3) Ideal Sampler Fractional...

  4. 40 CFR Table F-5 to Subpart F of... - Estimated Mass Concentration Measurement of PM 2.5 for Idealized “Typical” Coarse Aerosol Size...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Estimated Mass Concentration... 53—Estimated Mass Concentration Measurement of PM 2.5 for Idealized “Typical” Coarse Aerosol Size... Concentration (µg/m 3) Estimated Mass Concentration Measurement (µg/m 3) Ideal Sampler Fractional...

  5. Atmospheric pressure flow reactor / aerosol mass spectrometer studies of tropospheric aerosol nucleat and growth kinetics. Final report, June, 2001

    SciTech Connect

    Worsnop, Douglas R.

    2001-06-01

    The objective of this program was to determine the mechanisms and rates of growth and transformation and growth processes that control secondary aerosol particles in both the clear and polluted troposphere. The experimental plan coupled an aerosol mass spectrometer (AMS) with a chemical ionization mass spectrometer to provide simultaneous measurement of condensed and particle phases. The first task investigated the kinetics of tropospheric particle growth and transformation by measuring vapor accretion to particles (uptake coefficients, including mass accommodation coefficients and heterogeneous reaction rate coefficients). Other work initiated investigation of aerosol nucleation processes by monitoring the appearance of submicron particles with the AMS as a function of precursor gas concentrations. Three projects were investigated during the program: (1) Ozonolysis of oleic acid aerosols as model of chemical reactivity of secondary organic aerosol; (2) Activation of soot particles by measurement deliquescence in the presence of sulfuric acid and water vapor; (3) Controlled nucleation and growth of sulfuric acid aerosols.

  6. Aerosol chemical composition in cloud events by high resolution time-of-flight aerosol mass spectrometry.

    PubMed

    Hao, Liqing; Romakkaniemi, Sami; Kortelainen, Aki; Jaatinen, Antti; Portin, Harri; Miettinen, Pasi; Komppula, Mika; Leskinen, Ari; Virtanen, Annele; Smith, James N; Sueper, Donna; Worsnop, Douglas R; Lehtinen, Kari E J; Laaksonen, Ari

    2013-03-19

    This study presents results of direct observations of aerosol chemical composition in clouds. A high-resolution time-of-flight aerosol mass spectrometer was used to make measurements of cloud interstitial particles (INT) and mixed cloud interstitial and droplet residual particles (TOT). The differences between these two are the cloud droplet residuals (RES). Positive matrix factorization analysis of high-resolution mass spectral data sets and theoretical calculations were performed to yield distributions of chemical composition of the INT and RES particles. We observed that less oxidized hydrocarbon-like organic aerosols (HOA) were mainly distributed into the INT particles, whereas more oxidized low-volatile oxygenated OA (LVOOA) mainly in the RES particles. Nitrates existed as organic nitrate and in chemical form of NH(4)NO(3). Organic nitrates accounted for 45% of total nitrates in the INT particles, in clear contrast to 26% in the RES particles. Meanwhile, sulfates coexist in forms of acidic NH(4)HSO(4) and neutralized (NH(4))(2)SO(4). Acidic sulfate made up 64.8% of total sulfates in the INT particles, much higher than 10.7% in the RES particles. The results indicate a possible joint effect of activation ability of aerosol particles, cloud processing, and particle size effects on cloud formation.

  7. Mass size distributions of elemental aerosols in industrial area

    PubMed Central

    Moustafa, Mona; Mohamed, Amer; Ahmed, Abdel-Rahman; Nazmy, Hyam

    2014-01-01

    Outdoor aerosol particles were characterized in industrial area of Samalut city (El-minia/Egypt) using low pressure Berner cascade impactor as an aerosol sampler. The impactor operates at 1.7 m3/h flow rate. Seven elements were investigated including Ca, Ba, Fe, K, Cu, Mn and Pb using atomic absorption technique. The mean mass concentrations of the elements ranged from 0.42 ng/m3 (for Ba) to 89.62 ng/m3 (for Fe). The mass size distributions of the investigated elements were bi-modal log normal distribution corresponding to the accumulation and coarse modes. The enrichment factors of elements indicate that Ca, Ba, Fe, K, Cu and Mn are mainly emitted into the atmosphere from soil sources while Pb is mostly due to anthropogenic sources. PMID:26644919

  8. Comparison of Aerosol Mass Spectrometer and Aerosol Chemical Speciation Monitor Measurements of Secondary Organic Aerosol Formation in Smog Chamber Studies

    NASA Astrophysics Data System (ADS)

    Croteau, P. L.; Hunter, J. F.; Daumit, K. E.; Carrasquillo, A. J.; Cross, E. S.; Canagaratna, M.; Jayne, J.; Worsnop, D. R.; Kroll, J. H.

    2012-12-01

    Thermal vaporization-electron impact ionization (TV-EI) mass spectrometry is a powerful tool for understanding the chemistry of secondary organic aerosol (SOA) formation and atmospheric aging. The Aerodyne Aerosol Mass Spectrometer (AMS) and recently developed Aerosol Chemical Speciation Monitor (ACSM) are two instruments that utilize the same TV-EI technique. The ACSM trades the particle sizing capability, sensitivity, speed, and resolution of the AMS for simplicity, affordability, and ease of operation - enabling stand-alone continuous sampling for extended periods of time. Here we present results of an intercomparison between a high-resolution AMS and an ACSM. Three well-studied SOA formation chamber experiments were conducted: isoprene photooxidation under high NOx conditions, m-xylene photooxidation under high NOx conditions, and α-pinene ozonolysis under low NOx conditions. Comparisons between time-series and mass spectra from these experiments, along with positive matrix factorization analysis results demonstrate that the ACSM, while it does not provide the same level of detail as an AMS, is a suitable tool for exploring the chemistry of SOA formation in chamber studies.

  9. Seasonal differences of urban organic aerosol composition - an ultra-high resolution mass spectrometry study

    NASA Astrophysics Data System (ADS)

    Rincon, A. G.; Calvo, A. I.; Dietzel, M.; Kalberer, M.

    2012-04-01

    The understanding of the chemical composition of atmospheric aerosols, their properties and reactivity are important for assessing aerosol effects upon both global climate change and human health. The composition of organic aerosols is poorly understood mainly due to their highly complex chemical composition with several thousand compounds. In the present study the water-soluble organic fraction of ambient particles collected at an urban site in Cambridge, UK, during different seasons were analysed with ultra-high resolution mass spectrometry. For several thousand peaks in the mass specta (between 3000-6000) an elemental composition could be assigned and summer samples generally contained more components than winter samples. Up to 80% of the peaks in the mass spectra contain nitrogen and/or sulphur functional groups and only about 20% of the compounds contain only C, H and O atoms. In summer the fraction of compounds with oxidized nitrogen and sulphur groups increases compared to winter indicating a photo-chemical formation route of these multifunctional compounds. In addition to oxidized nitrogen compounds a large number of highly unsaturated reduced nitrogen-containing compounds were detected, corresponding likely to cyclic amines. A significant number of oxidized PAHs have been detected in summer samples, which were not present in winter, indicating again photo-chemical aging processes. Both, amines and long-chain aliphatic acids (also frequently observed in these urban samples) are likely signatures of biomass burning and primary biological sources. Potential biomass burning markers are discussed. Particle-phase oligomerisation reactions have only been observed to a very limited degree. Compounds larger than m/z 350 almost exclusively contained N and/or S functional groups indicating that the high molecular weight compounds in these organic aerosol extracts might be mainly due to particle-phase heterogeneous reactions of organic compounds with inorganic

  10. Analysis of Organic Anionic Surfactants in Fine and Coarse Fractions of Freshly Emitted Sea Spray Aerosol.

    PubMed

    Cochran, Richard E; Laskina, Olga; Jayarathne, Thilina; Laskin, Alexander; Laskin, Julia; Lin, Peng; Sultana, Camille; Lee, Christopher; Moore, Kathryn A; Cappa, Christopher D; Bertram, Timothy H; Prather, Kimberly A; Grassian, Vicki H; Stone, Elizabeth A

    2016-03-01

    The inclusion of organic compounds in freshly emitted sea spray aerosol (SSA) has been shown to be size-dependent, with an increasing organic fraction in smaller particles. Here we have used electrospray ionization-high resolution mass spectrometry in negative ion mode to identify organic compounds in nascent sea spray collected throughout a 25 day mesocosm experiment. Over 280 organic compounds from ten major homologous series were tentatively identified, including saturated (C8-C24) and unsaturated (C12-C22) fatty acids, fatty acid derivatives (including saturated oxo-fatty acids (C5-C18) and saturated hydroxy-fatty acids (C5-C18), organosulfates (C2-C7, C12-C17) and sulfonates (C16-C22). During the mesocosm, the distributions of molecules within some homologous series responded to variations among the levels of phytoplankton and bacteria in the seawater. The average molecular weight and carbon preference index of saturated fatty acids significantly decreased within fine SSA during the progression of the mesocosm, which was not observed in coarse SSA, sea-surface microlayer or in fresh seawater. This study helps to define the molecular composition of nascent SSA and biological processes in the ocean relate to SSA composition. PMID:26828238

  11. Aerosols in Polluted versus Nonpolluted Air Masses: Long-Range Transport and Effects on Clouds.

    NASA Astrophysics Data System (ADS)

    Pueschel, R. F.; van Valin, C. C.; Castillo, R. C.; Kadlecek, J. A.; Ganor, E.

    1986-12-01

    To assess the influence of anthropogenic aerosols on the physics and chemistry of clouds in the northeastern United State, aerosol and cloud-drop size distributions, elemental composition of aerosols as a function of size, and ionic content of cloud water were measured on Whiteface Mountain, New York, during the summers of 1981 and 1982. In several case studies, the data were cross-correlated with different air mass types-background continental, polluted continental, and maritime-that were advected to the sampling site. The results are the following (1) Anthropogenic sources hundreds of kilometers upwind cause the small-particle (accumulation) mode number to increase from hundreds to thousands per cubic centimeter and the mass loading to increase from a few to several tens of micrograms per cubic meter, mostly in the form of sulfur aerosols. (ii) A significant fraction of anthropogenic sulfur aerosols appears to act as cloud condensation nuclei (CCN) to affect the cloud drop concentration. (iii) Clouds in Atlantic maritime air masses have cloud drop spectra that are markedly different from those measured in continental clouds. The drop concentration is significantly lower, and the drop size spectra are heavily skewed toward large drops. (iv) Effects of anthropogenic pollutants on cloud water ionic composition are an increase of nitrate by a factor of 50, an increase of sulfate by more than one order of magnitude, and an increase of ammonium ion by a factor of 7. The net effect of the changes in ionic concentrations is an increase in cloud water acidity. An anion deficit even in maritime clouds suggests an unknown, possibly biogenic, source that could be responsible for a pH below neutral, which is frequently observed in nonpolluted clouds.

  12. Speciation and water soluble fraction of iron in aerosols from various sources

    NASA Astrophysics Data System (ADS)

    Takahashi, Y.; Kurisu, M.; Uematsu, M.

    2015-12-01

    Iron (Fe) is an essential micronutrient and has been identified as a limiting factor for phytoplankton growth in high-nitrate low-chlorophyll (HNLC) regions of the ocean. In the North Pacific, three sources of iron (Fe) transported via. atmosphere can be suggested: (i) mineral dust from East Asia, (ii) anthropogenic Fe, and (iii) aerosols from volcanic origin. Considering these different sources, Fe can be found and transported in a variety of chemical forms, both water-soluble and -insoluble. It is generally believed that only the soluble fraction of Fe can be considered as bioavailable for phytoplankton. To assess the biogeochemical impact of the atmospheric input, attempt was made to determine Fe species by X-ray absorption spectroscopy (XAS) and its water solubility, in particular to compare the three sources. Iron species, chemical composition, and soluble Fe concentration in aerosol collected at Tsukuba (Japan) through a year were investigated to compare the contributions of mineral dust and anthropogenic components. It was found that the concentration of soluble Fe in aerosol is correlated with those of sulfate and oxalate which originate from anthropogenic sources, suggesting that soluble Fe is mainly derived from anthropogenic sources. XAS analysis showed that main Fe species in aerosols in Tsukuba were illite, ferrihydrite, hornblende, and Fe(III) sulfate. Moreover, soluble Fe fraction is closely correlated with that of Fe(III) sulfate. In spite of supply of high concentrations of Fe in mineral dust from East Asia, it was found that anthropogenic fraction is important due to its high water solubility by the presence of Fe(III) sulfate. Marine aerosol samples originated from volcanic ash were collected in the western North Pacific during KH-08-2 cruise (August, 2008). XAS analysis suggested that Fe species of volcanic ashes changed during the long-range transport, while dissolution experiment showed that Fe solubility of the marine aerosol is larger than

  13. Analysis of size-fractionated coal combustion aerosols by PIXE and other analytical techniques

    NASA Astrophysics Data System (ADS)

    Maenhaut, W.; Røyset, O.; Vadset, M.; Kauppinen, E. I.; Lind, T. M.

    1993-04-01

    Particle-induced X-ray emission (PIXE) analysis, instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS) were used to study the chemical composition of size-fractionated in-stack fly-ash particles emitted during coal combustion. The samples were collected before the electrostatic precipitator at a gas temperature of 120°C during the combustion of Venezuelan coal in a 81 MW capacity circulating fluidized bed boiler. The sampling device consisted of a Berner low pressure impactor, which was operated with a cyclone precutter. The Nuclepore polycarbonate foils, which were used as collection surfaces in the low pressure impactor, were analyzed by the three techniques and the results of common elements were critically compared. The PIXE results were systematically lower than the INAA data and the percentage difference appeared to be stage-dependent, but virtually independent upon the element. The discrepancies are most likely due to bounce-off effects, particle reentrainment and other sampling artifacts, which may make that a fraction of the aerosol particles is deposited on the impaction foils outside the section analyzed by PIXE. However, by resorting to a "mixed internal standard" approach, accurate PIXE data are obtained. Also in the comparison between the ICP-MS and the INAA data significant discrepancies were observed. These are most likely due to incomplete dissolution of the particulate material and in particular of the alumino-silicate fly-ash matrix, during the acid digestion sample preparation step for ICP-MS. It is suggested that a comparison between ICP-MS data of acid digested samples and INAA can advantageously be used to provide speciation information on the various elements. Selected examples of size distributions are presented and briefly discussed.

  14. Ambient Aerosol in Southeast Asia: High Resolution Aerosol Mass Spectrometer Measurements Over Oil Palm (Elaeis guineensis)

    NASA Astrophysics Data System (ADS)

    Phillips, G.; Dimarco, C.; Misztal, P.; Nemitz, E.; Farmer, D.; Kimmel, J.; Jimenez, J.

    2008-12-01

    The emission of organic compounds in the troposphere is important factor in the formation of secondary organic aerosol (SOA). A very large proportion of organic material emitted globally is estimated to arise from biogenic sources, with almost half coming from tropical and sub-tropical forests. Preliminary analyses of leave cuvette emission studies suggest that oil palm (Elaeis guineensis) is a significantly larger source of isoprene than tropical forest. Much larger sources of isoprene over oil palm allied with a larger anthropogenic component of local emissions contrast greatly with the remote tropical forest environment and therefore the character of SOA formed may differ significantly. These issues, allied with the high price of palm oil on international markets leading to increased use of land for oil palm production, could give rise to rapidly changing chemical and aerosol regimes in the tropics. It is therefore important to understand the current emissions and composition of organic aerosol over all important land-uses in the tropical environment. This in turn will lead to a greater understanding of the present, and to an improvement in predictive capacity for the future system. To help address these issues, a high resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) was deployed in the Sabahmas (PPB OIL) oil palm plantation near Lahad Datu, in Eastern Sabah, as part of the field component of the Aerosol Coupling in the Earth System (ACES) project, part of the UK NERC APPRAISE program. This project was allied closely with measurements made of similar chemical species and aerosol components at a forest site in the Danum Valley as part of the UK Oxidant and Particle Photochemical Processes above a Southeast Asian tropical rainforest (OP3) project. Measurements of submicron non- refractory aerosol composition are presented along with some preliminary analysis of chemically resolved aerosol fluxes made with a new eddy covariance system, based on the

  15. Detection of biological particles in ambient air using Bio-Aerosol Mass Spectrometry

    SciTech Connect

    McJimpsey, E L; Steele, P T; Coffee, K R; Fergenson, D P; Riot, V J; Woods, B W; Gard, E E; Frank, M; Tobias, H J; Lebrilla, C

    2006-03-16

    The Bio-Aerosol Mass Spectrometry (BAMS) system is an instrument used for the real time detection and identification of biological aerosols. Particles are drawn from the atmosphere directly into vacuum and tracked as they scatter light from several continuous wave lasers. After tracking, the fluorescence of individual particles is excited by a pulsed 266nm or 355nm laser. Molecules from those particles with appropriate fluorescence properties are subsequently desorbed and ionized using a pulsed 266nm laser. Resulting ions are analyzed in a dual polarity mass spectrometer. During two field deployments at the San Francisco International Airport, millions of ambient particles were analyzed and a small but significant fraction were found to have fluorescent properties similar to Bacillus spores and vegetative cells. Further separation of non-biological background particles from potential biological particles was accomplished using laser desorption/ionization mass spectrometry. This has been shown to enable some level of species differentiation in specific cases, but the creation and observation of higher mass ions is needed to enable a higher level of specificity across more species. A soft ionization technique, matrix-assisted laser desorption/ionization (MALDI) is being investigated for this purpose. MALDI is particularly well suited for mass analysis of biomolecules since it allows for the generation of molecular ions from large mass compounds that would fragment under normal irradiation. Some of the initial results from a modified BAMS system utilizing this technique are described.

  16. A new method for estimating aerosol mass flux in the urban surface layer using LAS technology

    NASA Astrophysics Data System (ADS)

    Yuan, Renmin; Luo, Tao; Sun, Jianning; Liu, Hao; Fu, Yunfei; Wang, Zhien

    2016-04-01

    Atmospheric aerosol greatly influences human health and the natural environment, as well as the weather and climate system. Therefore, atmospheric aerosol has attracted significant attention from society. Despite consistent research efforts, there are still uncertainties in understanding its effects due to poor knowledge about aerosol vertical transport caused by the limited measurement capabilities of aerosol mass vertical transport flux. In this paper, a new method for measuring atmospheric aerosol vertical transport flux is developed based on the similarity theory of surface layer, the theory of light propagation in a turbulent atmosphere, and the observations and studies of the atmospheric equivalent refractive index (AERI). The results show that aerosol mass flux can be linked to the real and imaginary parts of the atmospheric equivalent refractive index structure parameter (AERISP) and the ratio of aerosol mass concentration to the imaginary part of the AERI. The real and imaginary parts of the AERISP can be measured based on the light-propagation theory. The ratio of the aerosol mass concentration to the imaginary part of the AERI can be measured based on the measurements of aerosol mass concentration and visibility. The observational results show that aerosol vertical transport flux varies diurnally and is related to the aerosol spatial distribution. The maximum aerosol flux during the experimental period in Hefei City was 0.017 mg m-2 s-1, and the mean value was 0.004 mg m-2 s-1. The new method offers an effective way to study aerosol vertical transport in complex environments.

  17. Identification of characteristic mass spectrometric markers for primary biological aerosol particles and comparison with field data from submicron pristine aerosol particles

    NASA Astrophysics Data System (ADS)

    Freutel, F.; Schneider, J.; Zorn, S. R.; Drewnick, F.; Borrmann, S.; Hoffmann, T.; Martin, S. T.

    2009-04-01

    The contribution of primary biological aerosol (PBA) to the total aerosol particle concentration is estimated to range between 25 and 80%, depending on location and season. Especially in the tropical rain forest it is expected that PBA is a major source of particles in the supermicron range, and is also an important fraction of the submicron aerosol. PBA particles like plant fragments, pollen, spores, fungi, viruses etc. contain chemical compounds as proteins, sugars, amino acids, chlorophyll, and cellular material as cellulose. For this reason we have performed mass spectrometric laboratory measurements (Aerodyne C-ToF and W-ToF AMS, single particle laser ablation instrument SPLAT) on pure submicron aerosol particles containing typical PBA compounds in order to identify typical mass spectral patterns of these compounds and to explain the observed fragmentation patterns on the basis of molecular structures. These laboratory data were compared to submicron particle mass spectra obtained during AMAZE-08 (Amazonian Aerosol CharacteriZation Experiment, Brazil, February/March 2008). The results indicate that characteristic m/z ratios for carbohydrates (e.g., glucose, saccharose, levoglucosan, mannitol) can be identified, for example m/z = 60(C2H4O2+) or m/z = 61(C2H5O2+). Certain characteristic peaks for amino acids were also identified in the laboratory experiments. In the field data from AMAZE-08, these characteristic peaks for carbohydrates and amino acids were found, and their contribution to the total organic mass was estimated to about 5%. Fragment ions from peptides and small proteins were also identified in laboratory experiments. Larger proteins, however, seem to become oxidized to CO2+ to a large extend in the vaporizing process of the AMS. Thus, detection of proteins in atmospheric aerosol particles with the AMS appears to be difficult.

  18. Improving Calculation Accuracies of Accumulation-Mode Fractions Based on Spectral of Aerosol Optical Depths

    NASA Astrophysics Data System (ADS)

    Ying, Zhang; Zhengqiang, Li; Yan, Wang

    2014-03-01

    Anthropogenic aerosols are released into the atmosphere, which cause scattering and absorption of incoming solar radiation, thus exerting a direct radiative forcing on the climate system. Anthropogenic Aerosol Optical Depth (AOD) calculations are important in the research of climate changes. Accumulation-Mode Fractions (AMFs) as an anthropogenic aerosol parameter, which are the fractions of AODs between the particulates with diameters smaller than 1μm and total particulates, could be calculated by AOD spectral deconvolution algorithm, and then the anthropogenic AODs are obtained using AMFs. In this study, we present a parameterization method coupled with an AOD spectral deconvolution algorithm to calculate AMFs in Beijing over 2011. All of data are derived from AErosol RObotic NETwork (AERONET) website. The parameterization method is used to improve the accuracies of AMFs compared with constant truncation radius method. We find a good correlation using parameterization method with the square relation coefficient of 0.96, and mean deviation of AMFs is 0.028. The parameterization method could also effectively solve AMF underestimate in winter. It is suggested that the variations of Angstrom indexes in coarse mode have significant impacts on AMF inversions.

  19. Mass Spectrometry of Atmospheric Aerosol: 1 nanometer to 1 micron

    NASA Astrophysics Data System (ADS)

    Worsnop, D. R.; Ehn, M.; Junninen, H.; Kulmala, M. T.

    2010-12-01

    The role of aerosol particles remains the largest uncertainty in quantitatively assessing past, current and future climate change. The principal reason for that uncertainty arises from the need to characterize and model composition and size dependent aerosol processes, ranging from nanometer to micron scales. Aerosol mass spectrometry results have shown that about half the sub-micron aerosol composition is composed of highly oxygenated organics that are not well understood in terms of photochemical reaction mechanisms (Jimenez et al, 2009). This work has included application of high resolution time-of-flight mass spectrometry (ToFMS) in order to determine elemental and functional group composition of complex organic components. Recently, we have applied similar ToFMS to determine the composition of ambient ions, molecules and clusters, potentially involved in formation and growth of nano-particles (Junninen et al, 2010). Observed organic anions (molecular weight range 200-500 Th) have similar chemical composition as the least volatile secondary organics observed in fine particles; while organic cations are dominated by amines and pyridines. During nucleation events, anions are dominated by sulphuric acid cluster ions (Ehn et al, 2010). In both nanometer and micrometer size ranges, the goal to elucidate the roles of inorganic and organic species, particularly how particle evolution and physical properties depend on mixed compositions. Recent results will be discussed, including ambient and experimental chamber observations. Ehn et al, Atmos. Chem. Phys. Discuss., 10, 14897-14946, 2010 Jimenez et al, Science, 326, 1525-1529, 2009 Junninen et al, Atmos. Meas. Tech., 3, 1039-1053, 2010

  20. Characterization of primary organic aerosol emissions from meat cooking, trash burning, and motor vehicles with high-resolution aerosol mass spectrometry and comparison with ambient and chamber observations.

    PubMed

    Mohr, Claudia; Huffman, Alex; Cubison, Michael J; Aiken, Allison C; Docherty, Kenneth S; Kimmel, Joel R; Ulbrich, Ingrid M; Hannigan, Michael; Jimenez, Jose L

    2009-04-01

    Organic aerosol (OA) emissions from motor vehicles, meat-cooking and trash burning are analyzed here using a high-resolution aerosol mass spectrometer (AMS). High resolution data show that aerosols emitted by combustion engines and plastic burning are dominated by hydrocarbon-like organic compounds. Meat cooking and especially paper burning emissions contain significant fractions of oxygenated organic compounds; however, their unit-resolution mass spectral signatures are very similar to those from ambient hydrocarbon-like OA, and very different from the mass spectra of ambient secondary or oxygenated OA (OOA). Thus, primary OA from these sources is unlikelyto be a significant direct source of ambient OOA. There are significant differences in high-resolution tracer m/zs that may be useful for differentiating some of these sources. Unlike in most ambient spectra, all of these sources have low total m/z 44 and this signal is not dominated by the CO2+ ion. All sources have high m/z 57, which is low during high OOA ambient periods. Spectra from paper burning are similar to some types of biomass burning OA, with elevated m/z 60. Meat cooking aerosols also have slightly elevated m/z 60, whereas motor vehicle emissions have very low signal at this m/z.

  1. Urban air quality assessment using monitoring data of fractionized aerosol samples, chemometrics and meteorological conditions.

    PubMed

    Yotova, Galina I; Tsitouridou, Roxani; Tsakovski, Stefan L; Simeonov, Vasil D

    2016-01-01

    The present article deals with assessment of urban air by using monitoring data for 10 different aerosol fractions (0.015-16 μm) collected at a typical urban site in City of Thessaloniki, Greece. The data set was subject to multivariate statistical analysis (cluster analysis and principal components analysis) and, additionally, to HYSPLIT back trajectory modeling in order to assess in a better way the impact of the weather conditions on the pollution sources identified. A specific element of the study is the effort to clarify the role of outliers in the data set. The reason for the appearance of outliers is strongly related to the atmospheric condition on the particular sampling days leading to enhanced concentration of pollutants (secondary emissions, sea sprays, road and soil dust, combustion processes) especially for ultra fine and coarse particles. It is also shown that three major sources affect the urban air quality of the location studied-sea sprays, mineral dust and anthropogenic influences (agricultural activity, combustion processes, and industrial sources). The level of impact is related to certain extent to the aerosol fraction size. The assessment of the meteorological conditions leads to defining of four downwind patterns affecting the air quality (Pelagic, Western and Central Europe, Eastern and Northeastern Europe and Africa and Southern Europe). Thus, the present study offers a complete urban air assessment taking into account the weather conditions, pollution sources and aerosol fractioning.

  2. Investigating types and sources of organic aerosol in Rocky Mountain National Park using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L., Jr.

    2015-01-01

    The environmental impacts of atmospheric particles are highlighted in remote areas where visibility and ecosystem health can be degraded by even relatively low particle concentrations. Submicron particle size, composition, and source apportionment were explored at Rocky Mountain National Park using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer. This summer campaign found low average, but variable, particulate mass (PM) concentrations (max = 93.1 μg m-3, avg. = 5.13 ± 2.72 μg m-3) of which 75.2 ± 11.1% is organic. Low-volatility oxidized organic aerosol (LV-OOA, 39.3% of PM1 on average) identified using Positive Matrix Factorization appears to be mixed with ammonium sulfate (3.9% and 16.6% of mass, respectively), while semi-volatile OOA (27.6%) is correlated with ammonium nitrate (nitrate: 4.3%); concentrations of these mixtures are enhanced with upslope (SE) surface winds from the densely populated Front Range area, indicating the importance of transport. A local biomass burning organic aerosol (BBOA, 8.4%) source is suggested by mass spectral cellulose combustion markers (m/z 60 and 73) limited to brief, high-concentration, polydisperse events (suggesting fresh combustion), a diurnal maximum at 22:00 local standard time when campfires were set at adjacent summer camps, and association with surface winds consistent with local campfire locations. The particle characteristics determined here represent typical summertime conditions at the Rocky Mountain site based on comparison to ~10 years of meteorological, particle composition, and fire data.

  3. Investigating types and sources of organic aerosol in Rocky Mountain National Park using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L., Jr.

    2014-07-01

    The environmental impacts of atmospheric particles are highlighted in remote areas where visibility and ecosystem health can be degraded by even relatively low particle concentrations. Submicron particle size, composition, and source apportionment were explored at Rocky Mountain National Park using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer. This summer campaign found low average, but variable, particulate mass (PM) concentrations (max = 93.1 μg m-3, avg. = 5.13 ± 2.72 μg m-3) of which 75.2 ± 11.1% is organic. Low-volatility oxidized organic aerosol (LV-OOA, 39.3% of PM1 on average) identified using Positive Matrix Factorization appears to be mixed with ammonium sulfate (3.9 and 16.6% of mass, respectively), while semi-volatile OOA (27.6%) is correlated with ammonium nitrate (nitrate: 4.3%); concentrations of these mixtures are enhanced with upslope (SE) surface winds from the densely populated Front Range area, indicating the importance of transport. A local biomass burning organic aerosol (BBOA, 8.4%) source is suggested by mass spectral cellulose combustion markers (m/zs 60 and 73) limited to brief, high-concentration, polydisperse events (suggesting fresh combustion), a diurnal maximum at 22:00 local standard time (LST) when campfires were set at adjacent summer camps, and association with surface winds consistent with local campfire locations. The particle characteristics determined here represent typical summertime conditions at the Rocky Mountain site based on comparison to ∼10 years of meteorological, particle composition, and fire data.

  4. Overview of aerosol properties associated with air masses sampled by the ATR-42 during the EUCAARI campaign (2008)

    NASA Astrophysics Data System (ADS)

    Crumeyrolle, S.; Schwarzenboeck, A.; Roger, J. C.; Sellegri, K.; Burkhart, J. F.; Stohl, A.; Gomes, L.; Quennehen, B.; Roberts, G.; Weigel, R.; Villani, P.; Pichon, J. M.; Bourrianne, T.; Laj, P.

    2013-05-01

    Within the frame of the European Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) project, the Météo-France aircraft ATR-42 performed 22 research flights over central Europe and the North Sea during the intensive observation period in May 2008. For the campaign, the ATR-42 was equipped to study the aerosol physical, chemical, hygroscopic and optical properties, as well as cloud microphysics. For the 22 research flights, retroplume analyses along the flight tracks were performed with FLEXPART in order to classify air masses into five sectors of origin, allowing for a qualitative evaluation of emission influence on the respective air parcel. This study shows that the extensive aerosol parameters (aerosol mass and number concentrations) show vertical decreasing gradients and in some air masses maximum mass concentrations (mainly organics) in an intermediate layer (1-3 km). The observed mass concentrations (in the boundary layer (BL): between 10 and 30 μg m-3; lower free troposphere (LFT): 0.8 and 14 μg m-3) are high especially in comparison with the 2015 European norms for PM2.5 (25 μg m-3) and with previous airborne studies performed over England (Morgan et al., 2009; McMeeking et al., 2012). Particle number size distributions show a larger fraction of particles in the accumulation size range in the LFT compared to BL. The chemical composition of submicron aerosol particles is dominated by organics in the BL, while ammonium sulphate dominates the submicron aerosols in the LFT, especially in the aerosol particles originated from north-eastern Europe (~ 80%), also experiencing nucleation events along the transport. As a consequence, first the particle CCN acting ability, shown by the CCN/CN ratio, and second the average values of the scattering cross sections of optically active particles (i.e. scattering coefficient divided by the optical active particle concentration) are increased in the LFT compared to BL.

  5. 40 CFR Table F-4 to Subpart F of... - Estimated Mass Concentration Measurement of PM2.5 for Idealized Coarse Aerosol Size Distribution

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Estimated Mass Concentration... Concentration Measurement of PM2.5 for Idealized Coarse Aerosol Size Distribution Particle Aerodynamic Diameter (µm) Test Sampler Fractional Sampling Effectiveness Interval Mass Concentration (µg/m3) Estimated...

  6. 40 CFR Table F-4 to Subpart F of... - Estimated Mass Concentration Measurement of PM 2.5 for Idealized Coarse Aerosol Size Distribution

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Estimated Mass Concentration... Concentration Measurement of PM 2.5 for Idealized Coarse Aerosol Size Distribution Particle Aerodynamic Diameter (µm) Test Sampler Fractional Sampling Effectiveness Interval Mass Concentration (µg/m3) Estimated...

  7. 40 CFR Table F-6 to Subpart F of... - Estimated Mass Concentration Measurement of PM 2.5 for Idealized Fine Aerosol Size Distribution

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Estimated Mass Concentration... Concentration Measurement of PM 2.5 for Idealized Fine Aerosol Size Distribution Particle Aerodynamic Diameter (µm) Test Sampler Fractional Sampling Effectiveness Interval Mass Concentration (µg/m3) Estimated...

  8. 40 CFR Table F-6 to Subpart F of... - Estimated Mass Concentration Measurement of PM 2.5 for Idealized Fine Aerosol Size Distribution

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Estimated Mass Concentration... Concentration Measurement of PM 2.5 for Idealized Fine Aerosol Size Distribution Particle Aerodynamic Diameter (µm) Test Sampler Fractional Sampling Effectiveness Interval Mass Concentration (µg/m 3)...

  9. 40 CFR Table F-6 to Subpart F of... - Estimated Mass Concentration Measurement of PM2.5 for Idealized Fine Aerosol Size Distribution

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Estimated Mass Concentration... Concentration Measurement of PM2.5 for Idealized Fine Aerosol Size Distribution Particle Aerodynamic Diameter (µm) Test Sampler Fractional Sampling Effectiveness Interval Mass Concentration (µg/m3) Estimated...

  10. 40 CFR Table F-4 to Subpart F of... - Estimated Mass Concentration Measurement of PM 2.5 for Idealized Coarse Aerosol Size Distribution

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Estimated Mass Concentration... Concentration Measurement of PM 2.5 for Idealized Coarse Aerosol Size Distribution Particle Aerodynamic Diameter (µm) Test Sampler Fractional Sampling Effectiveness Interval Mass Concentration (µg/m 3)...

  11. 40 CFR Table F-5 to Subpart F of... - Estimated Mass Concentration Measurement of PM2.5 for Idealized “Typical” Coarse Aerosol Size...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 5 2011-07-01 2011-07-01 false Estimated Mass Concentration... 53—Estimated Mass Concentration Measurement of PM2.5 for Idealized “Typical” Coarse Aerosol Size Distribution Particle Aerodynamic Diameter (µm) Test Sampler Fractional Sampling Effectiveness Interval...

  12. Stratospheric sulfuric acid fraction and mass estimate for the 1982 volcanic eruption of El Chichon

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.

    1983-01-01

    The stratospheric sulfuric acid fraction and mass for the 1982 volcanic eruptions of El Chichon are investigated using data from balloon soundings at Laramie (41 deg N) and in southern Texas (27-29 deg N). The total stratospheric mass of these eruptions is estimated to be approximately 8 Tg about 6.5 months after the eruption with possibly as much as 20 Tg in the stratosphere about 45 days after the eruption. Observations of the aerosol in Texas revealed two primary layers, both highly volatile at 150 C. Aerosol in the upper layer at about 25 km was composed of an approximately 80 percent H2SO4 solution while the lower layer at approximately 18 km was composed of a 60-65 percent H2SO4 solution aerosol. It is calculated that an H2SO4 vapor concentration of at least 3 x 10 to the 7th molecules/cu cm is needed to sustain the large droplets in the upper layer. An early bi-modal nature in the size distribution indicates droplet nucleation from the gas phase during the first 3 months, while the similarity of the large particle profiles 2 months apart shows continued particle growth 6.5 months after the explosion.

  13. Aerosol characterization over the southeastern United States using high resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition, sources, and organic nitrates

    NASA Astrophysics Data System (ADS)

    Xu, L.; Suresh, S.; Guo, H.; Weber, R. J.; Ng, N. L.

    2015-04-01

    We deployed a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) to characterize the chemical composition of submicron non-refractory particles (NR-PM1) in the southeastern US. Measurements were performed in both rural and urban sites in the greater Atlanta area, GA and Centreville, AL for approximately one year, as part of Southeastern Center of Air Pollution and Epidemiology study (SCAPE) and Southern Oxidant and Aerosol Study (SOAS). Organic aerosol (OA) accounts for more than half of NR1 mass concentration regardless of sampling sites and seasons. Positive matrix factorization (PMF) analysis of HR-ToF-AMS measurements identified various OA sources, depending on location and season. Hydrocarbon-like OA (HOA) and cooking OA (COA) have important but not dominant contributions to total OA in urban sites. Biomass burning OA (BBOA) concentration shows a distinct seasonal variation with a larger enhancement in winter than summer. We find a good correlation between BBOA and brown carbon, indicating biomass burning is an important source for brown carbon, although an additional, unidentified brown carbon source is likely present at the rural Yorkville site. Isoprene-derived OA (Isoprene-OA) is only deconvolved in warmer months and contributes 18-36% of total OA. The presence of Isoprene-OA factor in urban sites is more likely from local production in the presence of NOx than transport from rural sites. More-oxidized and less-oxidized oxygenated organic aerosol (MO-OOA and LO-OOA, respectively) are dominant fractions (47-79%) of OA in all sites. MO-OOA correlates well with ozone in summer, but not in winter, indicating MO-OOA sources may vary with seasons. LO-OOA, which reaches a daily maximum at night, correlates better with estimated nitrate functionality from organic nitrates than total nitrates. Based on the HR-ToF-AMS measurements, we estimate that the nitrate functionality from organic nitrates

  14. Ambient Observations of Organic Nitrogen Compounds in Submicrometer Aerosols in New York Using High Resolution Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhou, S.; Ge, X.; Xu, J.; Sun, Y.; Zhang, Q.

    2015-12-01

    Organic nitrogen (ON) compounds, which include amines, nitriles, organic nitrates, amides, and N-containing aromatic heterocycles, are an important class of compounds ubiquitously detected in atmospheric particles and fog and cloud droplets. Previous studies indicate that these compounds can make up a significant fraction (20-80%) of the total nitrogen (N) content in atmospheric condensed phases and play important roles in new particle formation and growth and affecting the optical and hygroscopicity of aerosols. In this study, we report the observation of ON compounds in submicrometer particles (PM1) at two locations in New York based on measurements using Aerodyne high-resolution time-of-flight mass spectrometer (HR-ToF-AMS). One study was conducted as part of the US Department of Energy funded Aerosol Lifecyle - Intensive Operation Period (ALC-IOP) campaign at Brookhaven National Lab (BNL, 40.871˚N, 72.89˚W) in summer, 2011 and the other was conducted at the Queen's College (QC) in New York City (NYC) in summer, 2009. We observed a notable amount of N-containing organic fragment ions, CxHyNp+ and CxHyOzNp+, in the AMS spectra of organic aerosols at both locations and found that they were mainly associated with amino functional groups. Compared with results from lab experiments, the C3H8N+ at m/z = 58 was primarily attributed to trimethylamine. In addition, a significant amount of organonitrates was observed at BNL. Positive matrix factorization (PMF) analysis of the high resolution mass spectra (HRMS) of organic aerosols identified a unique nitrogen-enriched OA (NOA) factor with elevated nitrogen-to-carbon (N/C) at both BNL and QC. Analysis of the size distributions, volatility profiles, and correlations with external tracer indicates that acid-base reactions of amino compounds with sulfate and acidic gas were mainly responsible for the formation of amine salts. Photochemical production was also observed to play a role in the formation of NOA. Bivariate polar

  15. Molecular composition of organic aerosols in central Amazonia: an ultra-high-resolution mass spectrometry study

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Godoi, Ricardo H. M.; Connors, Sarah; Levine, James G.; Archibald, Alex T.; Godoi, Ana F. L.; Paralovo, Sarah L.; Barbosa, Cybelli G. G.; Souza, Rodrigo A. F.; Manzi, Antonio O.; Seco, Roger; Sjostedt, Steve; Park, Jeong-Hoo; Guenther, Alex; Kim, Saewung; Smith, James; Martin, Scot T.; Kalberer, Markus

    2016-09-01

    The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen- and/or sulfur-containing organic species contributed up to 60 % of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen- and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic-biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.

  16. Seasonal differences in aerosol water may reconcile AOT and surface mass measurements in the Southeast U.S.

    NASA Astrophysics Data System (ADS)

    Nguyen, T. K. V.; Ghate, V. P.; Carlton, A. M. G.

    2015-12-01

    Summertime aerosol optical thickness (AOT) in the Southeast U.S. is high and sharply enhanced (2-3 times) compared to wintertime AOT. This seasonal pattern is unique to the Southeast U.S. and is of particular interest because temperatures there have not warmed over the past 100 years, contrasting with trends in other U.S. regions. Some investigators hypothesize the Southeast temperature trend is due to secondary organic aerosols (SOA) formed from interactions of biogenic volatile organic compounds (BVOCs) and anthropogenic emissions that create a cooling haze. However, aerosol measurements made at the surface do not exhibit strong seasonal differences in mass or organic fraction to support this hypothesis. In this work, we attempt to reconcile the spatial and temporal distribution of AOT over the U.S. with surface mass measurements by examining trends in particle-phase liquid water, an aerosol constituent that effectively scatters radiation and is removed from aerosols in mass measurements at routine surface monitoring sites. We employ the thermodynamic model ISORROPIA (v2.1) to estimate surface and aloft aerosol water mass concentrations at locations of Interagency Monitoring of Protected Visual Environments (IMPROVE) sites using measured speciated ion mass concentrations and NCEP North American Regional Reanalysis (NARR) meteorological data. Results demonstrate strong seasonal differences in aerosol water in the eastern compared to the western part of the U.S., consistent with geographic patterns in AOT. The highest mean regional seasonal difference from 2000 to 2007 is 5.5 μg m-3 and occurs the Southeast, while the lowest is 0.44 μg m-3 and occurs in the dry Mountain West. Our findings suggest 1) similarity between spatial trends in aerosol water in the U.S. and previously published AOT data from the MODIS-TERRA instrument and 2) similar interannual trends in mean aerosol water and previously published interannual AOT trends from MISR, MODIS-TERRA, MODIS

  17. Aerosol Size Distribution, Composition, and Hygroscopicity Measurements During CSTRIPE Using an Aerosol Mass Spectrometer and a Dual Differential Mobility Analyzer

    NASA Astrophysics Data System (ADS)

    Bahreini, R.; Varutbangkul, V.; Conant, W. C.; Flagan, R. C.; Seinfeld, J. H.; Buzorius, G.; Jonsson, H. H.

    2003-12-01

    During July 2003, the CIRPAS Twin Otter aircraft was deployed in the CSTRIPE (Coastal STRatocumulus Imposed Perturbation Experiment) field experiment in order to quantify the effects of aerosols on the microphysics and dynamics of marine stratocumulus clouds. In order to characterize the effects of different aerosol types on stratocumulus clouds, various air masses were sampled, including local fire plumes, pollution over the San Joaquin valley, unperturbed marine stratocumulus clouds, and stratocumulus clouds perturbed by seeding flares. Some research flights were also dedicated to characterize the seeding flares in the clear sky. Measurements of aerosol mass distribution and composition, using an Aerodyne Aerosol Mass Spectrometer (AMS), and size distribution and hygroscopic behavior, using a Dual Differential Mobility Analyzer (Dual DMA) with one column at dry conditions and another at a relative humidity of approximately 70 percent, will be presented here. During a number of in-cloud sampling periods, the Counter-flow Virtual Impactor (CVI) was used to select and dry cloud droplets, which were then analyzed by the AMS and the Dual DMA. The AMS composition measurements showed that sulfate and organics comprised most of the mass of the non-refractory components of the aerosol. The DMA showed a mixture of unimodal and bimodal size distributions in most types of air masses. The air mass over the San Joaquin valley, however, showed strong evidence of freshly nucleated particles, with aerosol number concentrations often above 80,000 cm-3.

  18. A CLOSURE STUDY OF AEROSOL MASS CONCENTRATION MEASUREMENTS: COMPARISON OF VALUES OBTAINED WITH FILTERS AND BY DIRECT MEASUREMENTS OF MASS DISTRIBUTIONS. (R826372)

    EPA Science Inventory

    We compare measurements of aerosol mass concentrations obtained gravimetrically using Teflon coated glass fiber filters and by integrating mass distributions measured with the differential mobility analyzer–aerosol particle mass analyzer (DMA–APM) technique (Aero...

  19. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    NASA Astrophysics Data System (ADS)

    Heringa, M. F.; Decarlo, P. F.; Chirico, R.; Tritscher, T.; Clairotte, M.; Mohr, C.; Crippa, M.; Slowik, J. G.; Pfaffenberger, L.; Dommen, J.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.

    2011-10-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm) mass. Secondary organic aerosol (SOA) is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from α-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra in the m/z range 12-250 showing Pearson's r values >0.94 for the correlations between the different SOA types after 5 h of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxidized OA (SV-OOA) observed in the ambient aerosol. The atomic O : C ratios were found to be in the range of 0.25-0.55 with no major increase during the first 5 h of aging. On average, the diesel SOA showed the lowest O : C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions based on their carbon number revealed that the SOA source with the highest O : C ratio had the largest fraction of small ions. Fragment ions containing up to 3 carbon atoms accounted for 66%, 68%, 72% and 76% of the organic spectrum of the SOA produced by the diesel car, wood burner, α-pinene and

  20. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    NASA Astrophysics Data System (ADS)

    Heringa, M. F.; Decarlo, P. F.; Chirico, R.; Tritscher, T.; Clairotte, M.; Mohr, C.; Crippa, M.; Slowik, J. G.; Pfaffenberger, L.; Dommen, J.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.

    2012-02-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm) mass. Secondary organic aerosol (SOA) is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from α-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA) observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25-0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions. The HR data of the four sources could be clustered and separated using principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate

  1. Mass fractionation of the lunar surface by solar wind sputtering

    NASA Technical Reports Server (NTRS)

    Switkowski, Z. E.; Haff, P. K.; Tombrello, T. A.; Burnett, D. S.

    1975-01-01

    The sputtering of the lunar surface by the solar wind is examined as a possible mechanism of mass fractionation. Simple arguments based on current theories of sputtering and the ballistics of the sputtered atoms suggest that most ejected atoms will have sufficiently high energy to escape lunar gravity. However, the fraction of atoms which falls back to the surface is enriched in the heavier atomic components relative to the lighter ones. This material is incorporated into the heavily radiation-damaged outer surfaces of grains where it is subject to resputtering. Over the course of several hundred years an equilibrium surface layer, enriched in heavier atoms, is found to form. The dependence of the calculated results upon the sputtering rate and on the details of the energy spectrum of sputtered particles is investigated. It is concluded that mass fractionation by solar wind sputtering is likely to be an important phenomenon on the lunar surface.

  2. Determination of the bioaccessible fraction of metals in urban aerosol using simulated lung fluids

    NASA Astrophysics Data System (ADS)

    Coufalík, Pavel; Mikuška, Pavel; Matoušek, Tomáš; Večeřa, Zbyněk

    2016-09-01

    Determination of the bioaccessible fraction of metals in atmospheric aerosol is a significant issue with respect to air pollution in the urban environment. The aim of this work was to compare of metal bioaccessibility determined according to the extraction yields of six simulated lung fluids. Aerosol samples of the PM1 fraction were collected in Brno, Czech Republic. The total contents of Cd, Ce, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn in the samples were determined and their enrichment factors were calculated. The bioaccessible proportions of elements were determined by means of extraction in Gamble's solution, Gamble's solution with dipalmitoyl phosphatidyl choline (DPPC), artificial lysosomal fluid, saline, water, and in a newly proposed solution based on DPPC, referred to as "Simulated Alveoli Fluid" (SAF). The chemical composition and surface tension of the simulated lung fluids were the main parameters influencing extraction yields. Gamble's solutions and the newly designed solution of SAF exhibited the lowest extraction efficiency, and also had the lowest surface tensions. The bioaccessibility of particulate metals should be assessed by synthetic lung fluids with a low surface tension, which simulate better the behavior and composition of native lung surfactant. The bioaccessibility of metals in aerosol assessed by means of the extraction in water or artificial lysosomal fluid can be overestimated.

  3. Bio-Aerosol Detection Using Mass Spectrometry: Public Health Applications

    SciTech Connect

    Ludvigson, Laura D.

    2004-01-01

    I recently spent a summer as an intern at the Lawrence Livermore National Laboratory. I worked on a project involving the real-time, reagentless, single cell detection of aerosolized pathogens using a novel mass spectrometry approach called Bio-Aerosol Mass Spectrometry (BAMS). Based upon preliminary results showing the differentiation capabilities of BAMS, I would like to explore the development and use of this novel detection system in the context of both environmental and clinical sample pathogen detection. I would also like to explore the broader public health applications that a system such as BAMS might have in terms of infectious disease prevention and control. In order to appreciate the potential of this instrument, I will demonstrate the need for better pathogen detection methods, and outline the instrumentation, data analysis and preliminary results that lead me toward a desire to explore this technology further. I will also discuss potential experiments for the future along with possible problems that may be encountered along the way.

  4. Comparative Analysis of Urban Atmospheric Aerosol by Particle-Induced X-ray Emission (PIXE), Proton Elastic Scattering Analysis (PESA), and Aerosol Mass Spectrometry (AMS)

    SciTech Connect

    Johnson, Kirsten S; Laskin, Alexander; Jimenez, Jose L; Shutthanandan, V; Molina, Luisa T; Salcedo, D; Dzepina, K; Molina, Mario J

    2008-09-01

    A multifaceted approach to atmospheric aerosol analysis is often desirable in field studies where an understanding of technical comparability among different measurement techniques is essential. Herein we report quantitative intercomparisons of Particle-Induced X-ray Emission (PIXE) and Proton Elastic Scattering Analysis (PESA), performed off-line under vacuum, with analysis by Aerosol Mass Spectrometry (AMS) carried out in real-time during the MCMA-2003 Field Campaign in the Mexico City Metropolitan Area. Good agreement was observed for mass concentrations of PIXE-measured sulfur (assuming it was dominated by SO42-) and AMS-measured sulfate during the most of the campaign. PESA-measured hydrogen mass was separated into sulfate H and organic H mass fractions assuming the only major contributions were (NH4)2SO4 and organic compounds. Comparison of the organic H mass with AMS organic aerosol measurements indicates that about 75% of the mass of these species evaporated under vacuum. However ~25% of the organics does remain under vacuum, which is only possible with low vapor pressure compounds, and which supports the presence of high molecular weight and/or highly oxidized organics consistent with atmospheric aging. Approximately 10% of the chloride detected by AMS was measured by PIXE, possibly in the form of metal-chloride complexes, while the majority of Cl was likely present as more volatile species including NH4Cl. This is the first comparison of PIXE/PESA and AMS, and to our knowledge also the first report of PESA hydrogen measurements for urban organic aerosols.

  5. Laboratory and field measurements of organic aerosols with the photoionization aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Dreyfus, Matthew A.

    Analytical methods developed to sample and characterize ambient organic aerosols often face the trade-off between long sampling times and the loss of detailed information regarding specific chemical species present. The soft, universal ionization scheme of the Photoionization Aerosol Mass Spectrometer (PIAMS) allows for identification of various chemical compounds by a signature ion, often the molecular ion. The goal of this thesis work is to apply PIAMS to both laboratory and field experiments to answer questions regarding the formation, composition, and behavior of organic aerosols. To achieve this goal, a variety of hardware and software upgrades were administered to PIAMS to optimize the instrument. Data collection and processing software were either refined or built from the ground up to simplify difficult or monotonous tasks. Additional components were added to PIAMS with the intent to automate the instrument, enhance the results, and make the instrument more rugged and user-friendly. These changes, combined with the application of an external particle concentration system (mini-Versatile Aerosol Concentration Enrichment System, m-VACES), allowed PIAMS to be suitable for field measurements of organic aerosols. Two such field campaigns were completed, both at the State of Delaware Air Quality Monitoring Site in Wilmington, Delaware: a one week period in June, 2006, and an 18 day period in October and November of 2007. A sampling method developed was capable of collecting sufficient ambient organic aerosol and analyzing it with a time resolution of 3.5 minutes. Because of this method, short term concentration changes of individual species can be tracked. Combined with meteorological data, the behavior of these species can be analyzed as a function of time or wind direction. Many compounds are found at enhanced levels during the evening/night-time hours; potentially due to the combined effects of temperature inversion, and fresh emissions in a cooler environment

  6. Influence of mass transfer on stable isotope fractionation.

    PubMed

    Thullner, Martin; Fischer, Anko; Richnow, Hans-Hermann; Wick, Lukas Y

    2013-01-01

    Biodegradation of contaminants is a common remediation strategy for subsurface environments. To monitor the success of such remediation means a quantitative assessment of biodegradation at the field scale is required. Nevertheless, the reliable quantification of the in situ biodegradation process it is still a major challenge. Compound-specific stable isotope analysis has become an established method for the qualitative analysis of biodegradation in the field and this method is also proposed for a quantitative analysis. However, to use stable isotope data to obtain quantitative information on in situ biodegradation requires among others knowledge on the influence of mass transfer processes on the observed stable isotope fractionation. This paper reviews recent findings on the influence of mass transfer processes on stable isotope fractionation and on the quantitative interpretation of isotope data. Focus will be given on small-scale mass transfer processes controlling the bioavailability of contaminants. Such bioavailability limitations are known to affect the biodegradation rate and have recently been shown to affect stable isotope fractionation, too. Theoretical as well as experimental studies addressing the link between bioavailability and stable isotope fractionation are reviewed and the implications for assessing biodegradation in the field are discussed.

  7. Mixing state of ambient aerosols in Nanjing city by single particle mass spectrometry

    NASA Astrophysics Data System (ADS)

    Wang, Honglei; An, Junlin; Shen, Lijuan; Zhu, Bin; Xia, Li; Duan, Qing; Zou, Jianan

    2016-05-01

    To investigate the mixing state and size-resolved aerosol in Nanjing, measurements were carried out for the period 14th January-1st February 2013 by using a Single Particle Aerosol Mass Spectrometer (SPAMS). A total of 10,864,766 particles were sized with vacuum aerodynamic diameter (dva) in the range of 0.2-2.0 μm. Of which, 1,989,725 particles were successfully ionized. Aerosol particles employed for analyzing SPAMS data utilized 96% of the hit particles to identify 5 main particle groups. The particle classes include: K-rich particles (K-CN, K-Nitrate, K-Sulfate and K-Secondary), sodium particles, ammonium particles, carbon-rich particles (OC, EC and OCEC) and heavy-metal particles (Fe-Secondary, Pb-Nitrate, Cu-Mn-Secondary and V-Secondary). EC was the largest contributor with a fraction of 21.78%, followed by K-Secondary (17.87%), K-Nitrate (12.68%) and K-CN (11.25%). High particle level and high RH (relative humidity) are two important factors decreasing visibility in Nanjing. Different particle classes have distinct extinction effects. It anti-correlated well with visibility for the K-secondary, sodium, ammonium, EC, Fe-Secondary and K-Nitrate particles. The proportion of EC particles at 0.65-1.4 μm was up to 25% on haze days and was below 10% on clean days.

  8. In situ acidity and pH of size-fractionated aerosols during a recent smoke-haze episode in Southeast Asia.

    PubMed

    Behera, Sailesh N; Cheng, Jinping; Balasubramanian, Rajasekhar

    2015-10-01

    The characterization of aerosol acidity has received increased attention in recent years due to its influence on atmospheric visibility, climate change and human health. Distribution of water soluble inorganic (WSI) ions in 12 different size fractions of aerosols was investigated under two different atmospheric conditions (smoke-haze and non-haze periods) in 2012 using the Micro-Orifice Uniform Deposit Impactor (MOUDI) and nano-MOUDI for the first time in Singapore. To estimate the in situ acidity ([H(+)]Ins) and in situ aerosol pH (pHIS), the Aerosol Inorganic Model version-IV under deliquescent mode of airborne particles was used at prevailing ambient temperature and relative humidity. The study revealed an increase in the levels of airborne particulate matter (PM) mass and concentrations of WSI ions for all size fractions during the smoke-haze period, which was caused by the trans-boundary transport of biomass burning-impacted air masses from Indonesia. A bimodal distribution was observed for concentrations of SO4(2-), NO3(-), Cl(-), K(+) and Na(+), whereas concentrations of NH4(+), Ca(2+) and Mg(2+) showed a single mode distribution. The concentration of WSI ions in PM1.8 during the smoke-haze period increased by 3.8 (for SO4(2-)) to 10.5 (for K(+)) times more than those observed during the non-haze period. The pHIS were observed to be lower during the smoke-haze period than that during the non-haze period for all size fractions of PM, indicating that atmospheric aerosols were more acidic due to the influence of biomass burning emissions. The particles in the accumulation mode were more acidic than those in the coarse mode.

  9. In situ acidity and pH of size-fractionated aerosols during a recent smoke-haze episode in Southeast Asia.

    PubMed

    Behera, Sailesh N; Cheng, Jinping; Balasubramanian, Rajasekhar

    2015-10-01

    The characterization of aerosol acidity has received increased attention in recent years due to its influence on atmospheric visibility, climate change and human health. Distribution of water soluble inorganic (WSI) ions in 12 different size fractions of aerosols was investigated under two different atmospheric conditions (smoke-haze and non-haze periods) in 2012 using the Micro-Orifice Uniform Deposit Impactor (MOUDI) and nano-MOUDI for the first time in Singapore. To estimate the in situ acidity ([H(+)]Ins) and in situ aerosol pH (pHIS), the Aerosol Inorganic Model version-IV under deliquescent mode of airborne particles was used at prevailing ambient temperature and relative humidity. The study revealed an increase in the levels of airborne particulate matter (PM) mass and concentrations of WSI ions for all size fractions during the smoke-haze period, which was caused by the trans-boundary transport of biomass burning-impacted air masses from Indonesia. A bimodal distribution was observed for concentrations of SO4(2-), NO3(-), Cl(-), K(+) and Na(+), whereas concentrations of NH4(+), Ca(2+) and Mg(2+) showed a single mode distribution. The concentration of WSI ions in PM1.8 during the smoke-haze period increased by 3.8 (for SO4(2-)) to 10.5 (for K(+)) times more than those observed during the non-haze period. The pHIS were observed to be lower during the smoke-haze period than that during the non-haze period for all size fractions of PM, indicating that atmospheric aerosols were more acidic due to the influence of biomass burning emissions. The particles in the accumulation mode were more acidic than those in the coarse mode. PMID:25432456

  10. Aerosol Composition in the Los Angeles Basin Studied by High Resolution Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Hayes, P. L.; Ortega, A. M.; Cubison, M.; Hu, W.; Toohey, D. W.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; Alvarez, S. L.; Rappenglueck, B.; Allan, J. D.; Taylor, J.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; De Gouw, J. A.; Massoli, P.; Zhang, X.; Weber, R.; Zhao, Y.; Cliff, S. S.; Wexler, A. S.; Isaacman, G. A.; Worton, D. R.; Kreisberg, N. M.; Hering, S. V.; Goldstein, A. H.; Jimenez, J. L.

    2011-12-01

    Atmospheric aerosols impact climate and health, but their sources and composition are poorly understood. To address this knowledge gap, a high-resolution aerosol mass spectrometer (AMS) and complementary instrumentation were deployed during the 2010 CalNex campaign to characterize aerosol composition in the Los Angeles (LA) area. Total mass concentrations as well as the species concentrations measured by the AMS compare well with most other instruments. Nitrate dominates in the mornings, but its concentration is reduced in the afternoon when organic aerosols (OA) increase and dominate. The diurnal variations in concentrations are strongly influenced by emission transport from the source-rich western basin. The average OA to enhanced CO ratio increases with photochemical age from 25 to 80 μg m-3 ppm-1, which indicates significant secondary OA (SOA) production and that a large majority of OA is secondary in aged air. The ratio values are similar to those from Mexico City as well as New England and the Mid-Atlantic States. Positive matrix factorization (PMF) is used to assess the concentrations of different OA components. The major OA classes are oxygenated OA (OOA, a surrogate for total SOA), and hydrocarbon-like OA (HOA, a surrogate for primary combustion OA). Several subclasses of OA are identified as well including diesel-influenced HOA (DI-HOA) and non-diesel HOA. DI-HOA exhibits low concentrations on Sundays consistent with the well-known weekday/weekend effect in LA. PMF analysis finds that OOA is 67% of the total OA concentration. A strong correlation between OOA and Ox (O3 + NO2) concentrations is observed with a slope of 0.15 that suggests the production of fresh SOA in Pasadena. Plotting the OA elemental ratios in a Van Krevelen diagram (H:C vs. O:C) yields a slope of -0.6, which is less steep than that observed in Riverside during the SOAR-2005 campaign. The difference in slopes may be attributed to the highly oxidized HOA present in Pasadena that is

  11. Characterization of Primary Organic Aerosol Emissions from Meat Cooking, Trash Burning, and Combustion Engines with High-Resolution Aerosol Mass Spectrometry and Comparison with Ambient and Chamber Observations

    NASA Astrophysics Data System (ADS)

    Mohr, C.; Huffman, J. A.; Cubison, M. J.; Aiken, A. C.; Docherty, K. S.; Kimmel, J. R.; Ulbrich, I. M.; Hannigan, M.; Garcia, J.; Jimenez, J. L.

    2009-04-01

    Organic aerosol (OA) emissions from motor vehicles, meat-cooking and trash burning are analyzed here using a high-resolution aerosol mass spectrometer (AMS) and supporting instrumentation. A semi-quantitative comparison of emission factors highlights the potential importance of meat cooking as an OA source. GC-MS and AMS mass spectra are compared for the first time and show high similarity, but with more fragmentation in the AMS due to higher vaporization temperatures. High resolution data show that aerosols emitted by combustion engines and plastic burning are dominated by hydrocarbon-like organic compounds. Meat cooking and especially paper burning contain significant fractions of oxygenated organic compounds; however, their unit-resolution mass spectral signatures are very similar to mass spectral signatures from hydrocarbon-like OA or primary OA, and very different from the mass spectra of ambient secondary or oxygenated OA (OOA). Thus, primary OA from any of these sources is very unlikely to be a significant direct source of ambient OOA. There are significant differences in high-resolution tracer m/z's that may be useful for differentiating these sources from each other. Unlike in most ambient spectra, all of these sources have low total m/z 44 and this signal is not dominated by the CO2+ ion. All sources have high m/z 57, which is low during high OOA ambient periods. Spectra from paper burning are similar to some types of biomass burning OA, with elevated m/z 60. Meat cooking aerosols also have slightly elevated m/z 60, while motor vehicle emissions have very low signal at this m/z.

  12. Mass Analysis of Charged Aerosol Particles During the MASS/ECOMA Campaign

    NASA Astrophysics Data System (ADS)

    Knappmiller, S.; Robertson, S.; Horanyi, M.; Sternovsky, Z.

    2008-12-01

    . The Mesospheric Aerosol Sampling Spectrometer (MASS) instrument was launched on two sounding rockets in August 2007 from Andoya, Norway to find the masses of charged aerosol particles in the polar mesosphere in NLC/PMSE conditions (3 August) and PMSE conditions alone (6 August). We compare and contrast the four data sets from the uplegs and downlegs. The MASS instrument collected ions, cluster ions, and charged nanometer-sized particles on four pairs of electrically-biased graphite plates that collect positive and negative particles separately. Electron collection was prevented by the negative potential on the rocket body. For the 3 August upleg, the data show charged particle collection on all channels with number densities of order several thousand per cubic centimeter in the four size ranges < 0.5 nm, 0.5-1 nm, 1-2 nm, and > 3 nm. The occurrence of positively charged aerosol particles in the smallest sizes suggests positive ions as the nucleation sites because the smallest particles have negligible probability of charging by photoionization. The signals were smaller on the 3 August downleg as a consequence of the spatial variability of the cloud. For the 6 August upleg into PMSE alone, only smaller particles (< 2 nm) were detected and these were both positive and negative with number densities of several thousand per cubic centimeter. On the downleg, 1-2 nm negatively charged particles were detected, but there were no positive particles in this mass range.

  13. Stable strontium mass dependent isotopic fractionation in authigenic continental barite

    NASA Astrophysics Data System (ADS)

    Griffith, E. M.; Widanagamage, I. H.; Scher, H. D.; Senko, J.

    2013-12-01

    The use of stable Sr-isotopic measurements (δ88Sr) of barite precipitates from terrestrial environments will be evaluated as a new geochemical proxy to identify mode of barite mineralization for use in earth science applications including understanding similar ancient barite deposits. Stable Sr-isotope measurements of barite and waters from three warm artesian springs in the continental United States where barite precipitates under a variety of conditions (e.g., temperatures, saturation states, microbial communities) will be presented. Initial results show a large range of fractionation factors during barite precipitation from aqueous solution between and within some of the field sites of >0.6 permil. The waters range from δ88Sr = -0.04 to +0.50 permil. The solid barite precipitates that have been separated from the bulk sediment using a modified sequential leaching procedure range from δ88Sr = -0.43 to +0.16 permil. Average 2σ for the isotopic analyses is 0.05 permil, similar to previously published estimates for error on this measurement by MC-ICPMS. Barite is a highly stable and widely-distributed mineral found in magmatic, metamorphic, and sedimentary rocks (of all ages), as well as in soils, aerosol dust, and extraterrestrial material. Establishing the controlling parameters of stable Sr-isotopic fractionation in barite is important as barite may be an ideal vehicle to address critical questions in the earth sciences, including early earth biogeochemistry.

  14. Elemental Composition of Primary Aerosols Emitted from Burning of 21 Biomass Fuels Measured by Aerosol Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Desyaterik, Y.; Mack, L.; Lee, T.; Kreidenweis, S. M.; Collett, J. L.; Jimenez, J. L.; Worsnop, D. R.

    2010-12-01

    Biomass burning emissions are an important contributor to regional aerosol loading and have a large impact of on air quality, visibility, and radiative forcing. However, the detailed chemical composition of the aerosols emitted during biomass burning is largely unknown. In order to gain a better understanding of the chemical and physical properties of these emissions, 92 burns were undertaken in the combustion chamber of the USDA/FS Fire Sciences Laboratory in Missoula, Montana, in well-defined laboratory conditions. A set of 21 different fuels was tested that represents biomass burned annually in the western and southeastern U.S. The chemical composition of the resulting biomass smoke aerosols was analyzed with a high-resolution aerosol mass spectrometer (Aerodyne HR-ToF-AMS). Simultaneous measurements of CO2 and CO concentrations allowed flaming and smoldering fire regimes to be distinguished. The elemental composition of the organic portion of the aerosols was extracted from the AMS measurements. Here we present the variation of O/C, H/C and organic mass to organic carbon ratios (OM/OC) versus fire regime and fuel type. We also discuss the influence on the organic aerosol chemical composition of various factors such as fuel moisture content and total aerosol loading, as well as the approach used to account for water vapor ions derived from water originally present in sampled particles versus water vapor ions produced by electron impact fragmentation of organic molecules.

  15. Low-energy ion implantation: Large mass fractionation of argon

    NASA Technical Reports Server (NTRS)

    Ponganis, K. V.; Graf, TH.; Marti, K.

    1993-01-01

    The isotropic signatures of noble gases in the atmospheres of the Earth and other planets are considerably evolved when compared to signatures observed in the solar wind. The mechanisms driving the evolution of planetary volatiles from original compositions in the solar accretion disk are currently poorly understood. Modeling of noble-gas compositional histories requires knowledge of fractionating processes that may have operated through the evolutionary stages. Since these gases are chemically inert, information on noble-gas fractionation processes can be used as probes. The importance of understanding these processes extends well beyond 'noble-gas planetology.' Trapped argon acquired by low-energy implantation (approximately less than 100 eV) into solids is strongly mass fractionated (approximately greater than or equal to 3 percent/amu). This has potential implications for the origin and evolution of terrestrial planet atmospheres.

  16. Carbonaceous and inorganic composition in long-range transported aerosols over northern Japan: Implication for aging of water-soluble organic fraction

    NASA Astrophysics Data System (ADS)

    Aggarwal, Shankar Gopala; Kawamura, Kimitaka

    To better understand the influence of sources and atmospheric processing on aerosol chemical composition, we collected atmospheric particles in Sapporo, northern Japan during spring and early summer 2005 under the air mass transport conditions from Siberia, China and surrounding seas. The aerosols were analyzed for inorganic ions, organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and the major water-soluble organic compound classes (i.e., dicarboxylic acids and sugars). SO 42- is the most abundant inorganic constituent (average 44% of the identified inorganic ion mass) followed by NH 4+ (21%) and NO 3- (13%). Concentrations of OC, EC, and WSOC ranged from 2.0-16, 0.24-2.9, and 0.80-7.9 μg m -3 with a mean of 7.4, 1.0, and 3.1 μg m -3, respectively. High OC/EC ratios (range: 3.6-19, mean: 8.7) were obtained, however WSOC/OC ratios (0.23-0.69, 0.44) do not show any significant diurnal changes. These results suggest that the Sapporo aerosols were already aged, but were not seriously affected by local photochemical processes. Identified water-soluble organic compounds (diacids + sugars) account for <10% of WSOC. Based on some marker species and air mass back trajectory analyses, and using stable carbon isotopic compositions of shorter-chain diacids (i.e., C 2-C 4) as photochemical aging factor of organic aerosols, the present study suggests that a fraction of WSOC in OC is most likely influenced by aerosol aging, although the OC loading in aerosols may be more influenced by their sources and source regions.

  17. Dynamics of Particle Size on Inhalation of Environmental Aerosol and Impact on Deposition Fraction.

    PubMed

    Haddrell, Allen E; Davies, James F; Reid, Jonathan P

    2015-12-15

    Inhalation of elevated levels of particulate air pollution has been shown to elicit the onset of adverse health effects in humans, where the magnitude of the response is a product of where in the lung the particulate dose is delivered. At any point in time during inhalation the depositional flux of the aerosol is a function of the radius of the droplet, thus a detailed understanding of the rate and magnitude of the mass flux of water to the droplet during inhalation is crucial. In this study, we assess the impact of aerosol hygroscopicity on deposited dose through the inclusion of a detailed treatment of the mass flux of water to account for the dynamics of particle size in a modified version of the standard International Commission on Radiological Protection (ICRP) whole lung deposition model. The ability to account for the role of the relative humidity (RH) of the aerosol prior to, and during, inhalation on the deposition pattern is explored, and found to have a significant effect on the deposition pattern. The model is verified by comparison to previously published measurements, and used to demonstrate that ambient RH affects where in the lung indoor particulate air pollution is delivered.

  18. [Retrieval of dust fraction of atmospheric aerosols based on spectra characteristics of refractive indices obtained from remote sensing measurements].

    PubMed

    Wang, Ling; Li, Zheng-Qiang; Li, Dong-Hui; Li, Kai-Tao; Tian, Qing-Jiu; Li, Li; Zhang, Ying; Lü, Yang; Gu, Xing-Fa

    2012-06-01

    Mineral dust is an important chemical component of aerosol, which has a significant impact on the climate and environmental changes. The spectral behavior of aerosol refractive indices at four wavelengths from 440 to 1 020 nm was analyzed based on one year observation obtained from Beijing AERONET site. The real parts of refractive index (n) in each band did not differ greatly, however the imaginary parts (k) showed a significant difference due to the absorption of mineral dust in aerosol. From 440 to 670 nm k decreased rapidly, while from 670 to 1 020 nm featured a lower, constant value. Accordingly, k(440 nm) could be considered separately with other three bands. Hence, we added mineral dust into the currently used three-component aerosol chemical model to form a new four-component model (i. e. BC, AS, dust and water) which is more suitable to represent the aerosol chemical composition. Then we presented a method to retrieve dust content in aerosols using this four-component model and refractive indices obtained from the sunphotometer measurements. Finally the dust content in aerosol was investigated under different weather conditions, i. e. clear, haze and dust in Beijing. The results showed that volume fractions of the dust component were 88%, 37% and 48% for clear, hazy and dusty day respectively, which was consistent with the coarse mode proportion in aerosols calculated from aerosol size distributions.

  19. The Effect of Solvent on the Analysis of Secondary Organic Aerosol Using Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Bateman, Adam P.; Walser, Maggie L.; Dessiaterik, Yury; Laskin, Julia; Laskin, Alexander; Nizkorodov, Serguei

    2008-08-29

    Solvent-analyte reactions in organic aerosol (OA) extracts prepared for analysis by electrospray ionization mass spectrometry (ESI-MS) were examined. Secondary organic aerosol (SOA) produced by ozonation of d-limonene as well as several test organic chemicals with functional groups typical for OA constituents were dissolved and stored in methanol, d3-methanol, acetonitrile, and d3-acetonitrile to investigate the extent and relative rates of reactions between analyte and solvent. High resolution ESI-MS showed that reactions of carbonyls with methanol produce significant amounts of hemiacetals and acetals on time scales ranging from several minutes to several days, with the reaction rates increasing in acidified solutions. Carboxylic acid groups were observed to react with methanol resulting in the formation of esters. In contrast, acetonitrile extracts showed no evidence of reactions with analyte molecules, suggesting that acetonitrile is the preferred solvent for SOA extraction. The use of solvent-analyte reactivity as an analytical chemistry tool for the improved characterization of functional groups in complex organic mixtures was also demonstrated. Direct comparison between ESI mass spectra of the same SOA samples extracted in reactive (methanol) versus non-reactive (acetonitrile) solvents was used to estimate the relative fractions of ketones (≥38%), aldehydes (≥6%), and carboxylic acids (≥55%) in d-limonene SOA.

  20. Secondary organic aerosol formation from in-use motor vehicle emissions using a potential aerosol mass reactor.

    PubMed

    Tkacik, Daniel S; Lambe, Andrew T; Jathar, Shantanu; Li, Xiang; Presto, Albert A; Zhao, Yunliang; Blake, Donald; Meinardi, Simone; Jayne, John T; Croteau, Philip L; Robinson, Allen L

    2014-10-01

    Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas.

  1. MISR Aerosol Air Mass Type Mapping over Mega-City: Validation and Applications

    NASA Astrophysics Data System (ADS)

    Patadia, F.; Kahn, R. A.

    2010-12-01

    Most aerosol air-quality monitoring in mega-city environments is done from scattered ground stations having detailed chemical and optical sampling capabilities. Satellite instruments such as the Multi-angle Imaging SpectroRadiometer (MISR) can retrieve total-column Aerosol Optical Depth (AOD), along with some information about particle microphysical properties. Although the particle property information from MISR is much less detailed than that obtained from the ground sampling stations, the coverage is extensive, making it possible to put individual surface observations into the context of regional aerosol air mass types. This paper presents an analysis of MISR aerosol observations made coincident with aircraft and ground-based instruments during the INTEX-B field campaign. These detailed comparisons of satellite aerosol property retrievals against dedicated field measurements provide the opportunity to validate the retrievals quantitatively at a regional level, and help to improve aerosol representation in retrieval algorithms. Validation of MISR retrieved AOD and other aerosol properties over the INTEX-B study region in and around Mexico City will be presented. MISR’s ability to distinguish among aerosol air mass types will be discussed. The goal of this effort is to use the MISR aerosol property retrievals for mapping both aerosol air mass type and AOD gradients in mega-city environments over the decade-plus that MISR has made global observations.

  2. Preliminary Results of Aerosol Chemical Composition Measurements in the Gulf of Maine with an Aerosol Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Middlebrook, A. M.; Canagaratna, M. R.; Worsnop, D. R.

    2002-12-01

    The New England Air Quality Study is a multi-institutional research project to improve understanding of the atmospheric processes that control the production and distribution of air pollutants in the New England region. During July-August, 2002 a large, collaborative, intensive period of atmospheric measurement and model comparisons took place. As part of this study, an Aerosol Mass Spectrometer (AMS) was deployed aboard the NOAA ship RONALD H. BROWN in the Gulf of Maine. The AMS measures semi-volatile components of aerosol particles with aerodynamic diameters between roughly 40 and 1500 nm. During this study, the AMS collected 2-minute averaged particle mass spectra as well as speciated organic, sulfate, and nitrate size distributions. Sodium chloride, sodium sulfate, and sodium nitrate components of the aerosol, which are relatively non-volatile at the AMS heater temperature, were not detected with the AMS. A wide variety of air masses were sampled during the intensive period, including clean marine, clean continental, and polluted continental air masses. In general, the volatile particle composition was mostly organic and sulfate with lesser amounts of nitrate. Furthermore, particle mass loadings typically peaked around 400-600 nm in aerodynamic diameter. Several events with high aerosol organic, sulfate, and/or nitrate mass loadings were observed and the atmospheric processes that cause them will be discussed.

  3. Microbial mass-dependent fractionation of chromium isotopes

    USGS Publications Warehouse

    Sikora, E.R.; Johnson, T.M.; Bullen, T.D.

    2008-01-01

    Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 ??M Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, 53Cr/52Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 ??M, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that 53Cr/52Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways. ?? 2008 Elsevier Ltd.

  4. Highly time-resolved urban aerosol characteristics during springtime in Yangtze River Delta, China: insights from soot particle aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Wang, Junfeng; Ge, Xinlei; Chen, Yanfang; Shen, Yafei; Zhang, Qi; Sun, Yele; Xu, Jianzhong; Ge, Shun; Yu, Huan; Chen, Mindong

    2016-07-01

    In this work, the Aerodyne soot particle - aerosol mass spectrometer (SP-AMS) was deployed for the first time during the spring of 2015 in urban Nanjing, a megacity in the Yangtze River Delta (YRD) of China, for online characterization of the submicron aerosols (PM1). The SP-AMS enables real-time and fast quantification of refractory black carbon (rBC) simultaneously with other non-refractory species (ammonium, sulfate, nitrate, chloride, and organics). The average PM1 concentration was found to be 28.2 µg m-3, with organics (45 %) as the most abundant component, following by sulfate (19.3 %), nitrate (13.6 %), ammonium (11.1 %), rBC (9.7 %), and chloride (1.3 %). These PM1 species together can reconstruct ˜ 44 % of the light extinction during this campaign based on the IMPROVE method. Chemically resolved mass-based size distributions revealed that small particles especially ultrafine ones (< 100 nm vacuum aerodynamic diameter) were dominated by organics and rBC, while large particles had significant contributions from secondary inorganic species. Source apportionment of organic aerosols (OA) yielded four OA subcomponents, including hydrocarbon-like OA (HOA), cooking-related OA (COA), semi-volatile oxygenated OA (SV-OOA), and low-volatility oxygenated OA (LV-OOA). Overall, secondary organic aerosol (SOA, equal to the sum of SV-OOA and LV-OOA) dominated the total OA mass (55.5 %), but primary organic aerosol (POA, equal to the sum of HOA and COA) can outweigh SOA in the early morning and evening due to enhanced human activities. High OA concentrations were often associated with high mass fractions of POA and rBC, indicating the important role of anthropogenic emissions during heavy pollution events. The diurnal cycles of nitrate, chloride, and SV-OOA both showed good anti-correlations with air temperatures, suggesting their variations were likely driven by thermodynamic equilibria and gas-to-particle partitioning. On the other hand, in contrast to other species

  5. Optical properties and chemical composition of aerosol particles at an urban location: An estimation of the aerosol mass scattering and absorption efficiencies

    NASA Astrophysics Data System (ADS)

    Titos, G.; Foyo-Moreno, I.; Lyamani, H.; Querol, X.; Alastuey, A.; Alados-Arboledas, L.

    2012-02-01

    We investigated aerosol optical properties, mass concentration and chemical composition over a 1 year period (from March 2006 to February 2007) at an urban site in Southern Spain (Granada, 37.18°N, 3.58°W, 680 m above sea level). Light-scattering and absorption measurements were performed using an integrating nephelometer and a MultiAngle Absorption Photometer (MAAP), respectively, with no aerosol size cut-off and without any conditioning of the sampled air. PM10 and PM1 (ambient air levels of atmospheric particulate matter finer than 10 and 1 microns) were collected with two high volume samplers, and the chemical composition was investigated for all samples. Relative humidity (RH) within the nephelometer was below 50% and the weighting of the filters was also at RH of 50%. PM10 and PM1 mass concentrations showed a mean value of 44 ± 19 μg/m3 and 15 ± 7 μg/m3, respectively. The mineral matter was the major constituent of the PM10-1 fraction (contributing more than 58%) whereas organic matter and elemental carbon (OM+EC) contributed the most to the PM1 fraction (around 43%). The absorption coefficient at 550 nm showed a mean value of 24 ± 9 Mm-1 and the scattering coefficient at 550 nm presented a mean value of 61 ± 25 Mm-1, typical of urban areas. Both the scattering and the absorption coefficients exhibited the highest values during winter and the lowest during summer, due to the increase in the anthropogenic contribution and the lower development of the convective mixing layer during winter. A very low mean value of the single scattering albedo of 0.71 ± 0.07 at 550 nm was calculated, suggesting that urban aerosols in this site contain a large fraction of absorbing material. Mass scattering and absorption efficiencies of PM10 particles exhibited larger values during winter and lower during summer, showing a similar trend to PM1 and opposite to PM10-1. This seasonality is therefore influenced by the variations on PM composition. In addition, the mass

  6. Determination of solid mass fraction in partially frozen hydrocarbon fuels

    NASA Technical Reports Server (NTRS)

    Cotterell, E. M.; Mossadegh, R.; Bruce, A. J.; Moynihan, C. T.

    1986-01-01

    Filtration procedures alone are insufficient to determine the amounts of crystalline solid in a partially frozen hydrocarbon distillate fraction. This is due to the nature of the solidification process by which a large amount of liquid becomes entrapped within an interconnected crystalline structure. A technique has been developed to supplement filtration methods with an independent determination of the amount of liquid in the precipitate thereby revealing the actual value of mass percent crystalline solid, %S. A non-crystallizing dye is injected into the fuel and used as a tracer during the filtration. The relative concentrations of the dye in the filtrate and precipitate fractions is subsequently detected by a spectrophotometric comparison. The filtration apparatus was assembled so that the temperature of the sample is recorded immediately above the filter. Also, a second method of calculation has been established which allows significant reduction in test time while retaining acceptable accuracy of results. Data have been obtained for eight different kerosene range hydrocarbon fuels.

  7. Direct measurements of mass-specific optical cross sections of single-component aerosol mixtures.

    PubMed

    Radney, James G; Ma, Xiaofei; Gillis, Keith A; Zachariah, Michael R; Hodges, Joseph T; Zangmeister, Christopher D

    2013-09-01

    The optical properties of atmospheric aerosols vary widely, being dependent upon particle composition, morphology, and mixing state. This diversity and complexity of aerosols motivates measurement techniques that can discriminate and quantify a variety of single- and multicomponent aerosols that are both internally and externally mixed. Here, we present a new combination of techniques to directly measure the mass-specific extinction and absorption cross sections of laboratory-generated aerosols that are relevant to atmospheric studies. Our approach employs a tandem differential mobility analyzer, an aerosol particle mass analyzer, cavity ring-down and photoacoustic spectrometers, and a condensation particle counter. This suite of instruments enables measurement of aerosol particle size, mass, extinction and absorption coefficients, and aerosol number density, respectively. Taken together, these observables yield the mass-specific extinction and absorption cross sections without the need to model particle morphology or account for sample collection artifacts. Here we demonstrate the technique in a set of case studies which involve complete separation of aerosol by charge, separation of an external mixture by mass, and discrimination between particle types by effective density and single-scattering albedo. PMID:23875772

  8. Contribution of isoprene-derived organosulfates to free tropospheric aerosol mass

    PubMed Central

    Froyd, K. D.; Murphy, S. M.; Murphy, D. M.; de Gouw, J. A.; Eddingsaas, N. C.; Wennberg, P. O.

    2010-01-01

    Recent laboratory studies have demonstrated that isoprene oxidation products can partition to atmospheric aerosols by reacting with condensed phase sulfuric acid, forming low-volatility organosulfate compounds. We have identified organosulfate compounds in free tropospheric aerosols by single particle mass spectrometry during several airborne field campaigns. One of these organosulfates is identified as the sulfate ester of IEPOX, a second generation oxidation product of isoprene. The patterns of IEPOX sulfate ester in ambient data generally followed the aerosol acidity and NOx dependence established by laboratory studies. Detection of the IEPOX sulfate ester was most sensitive using reduced ionization laser power, when it was observed in up to 80% of particles in the tropical free troposphere. Based on laboratory mass calibrations, IEPOX added > 0.4% to tropospheric aerosol mass in the remote tropics and up to 20% in regions downwind of isoprene sources. In the southeastern United States, when acidic aerosol was exposed to fresh isoprene emissions, accumulation of IEPOX increased aerosol mass by up to 3%. The IEPOX sulfate ester is therefore one of the most abundant single organic compounds measured in atmospheric aerosol. Our data show that acidity-dependent IEPOX uptake is a mechanism by which anthropogenic SO2 and marine dimethyl sulfide emissions generate secondary biogenic aerosol mass throughout the troposphere. PMID:21098310

  9. Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

    NASA Technical Reports Server (NTRS)

    Guzman, Marcelo I.; Athalye, Richa R.; Rodriguez, Jose M.

    2012-01-01

    During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ?Gdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp -2)) > (R(sub x-)(exp -1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8-8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol - and ethanol-water mixtures (0 <= xH2O <= 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I- on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I- < Br- < Cl- over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

  10. Concentration effects and ion properties controlling the fractionation of halides during aerosol formation.

    PubMed

    Guzman, Marcelo I; Athalye, Richa R; Rodriguez, Jose M

    2012-06-01

    During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO(2), NaNO(3), NaClO(4), and NaIO(4). The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f(X(-))) and their correlation with ion properties. Although no correlation exists between f(X(-)) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(X(-)), dehydration free-energy ΔG(dehyd), and polarizability α, follows the order: R(X(-))(-2) > R(X(-))(-1) > R(X(-)) > ΔG(dehyd) > α. The same pure physical process is observed in H(2)O and D(2)O. The factor f(X(-)) does not change with pH (6.8-8.6), counterion (Li(+), Na(+), K(+), and Cs(+)) substitution effects, or solvent polarity changes in methanol- and ethanol-water mixtures (0 ≤ x(H(2)O) ≤ 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I(-) on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I(-) < Br(-) < Cl(-) over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

  11. Detection of brake wear aerosols by aerosol time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Beddows, D. C. S.; Dall'Osto, M.; Olatunbosun, O. A.; Harrison, Roy M.

    2016-03-01

    Brake dust particles were characterised using an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) operated using two inlet configurations, namely the aerodynamic lens (AFL) inlet and countersunk nozzle inlet. Laboratory studies show that dust particles are characterised by mass spectra containing ions deriving from Fe and Ba and although highly correlated to each other, the Fe and Ba signals were mostly detected using the nozzle inlet with relatively high laser desorption energies. When using the AFL, only [56Fe] and [-88FeO2] ions were observed in brake dust spectra generated using lower laser desorption pulse energies, and only above 0.75 mJ was the [138Ba] ion detected. When used with the preferred nozzle inlet configuration, the [-88FeO2] peak was considered to be the more reliable tracer peak, because it is not present in other types of dust (mineral, tyre, Saharan etc). As shown by the comparison with ambient data from a number of locations, the aerodynamic lens is not as efficient in detecting brake wear particles, with less than 1% of sampled particles attributed to brake wear. Five field campaigns within Birmingham (background, roadside (3) and road tunnel) used the nozzle inlet and showed that dust particles (crustal and road) accounted for between 3.1 and 65.9% of the particles detected, with the remaining particles being made up from varying percentages of other constituents.

  12. Characteristics of aerosols and mass closure study at two WMO GAW regional background stations in eastern China

    NASA Astrophysics Data System (ADS)

    Yan, Peng; Zhang, Renjian; Huan, Ning; Zhou, Xiuji; Zhang, Yangmei; Zhou, Huaigang; Zhang, Leiming

    2012-12-01

    In the summer and winter of 2004 and 2005, size-segregated atmospheric aerosols were sampled with modified Andersen KA200 Multi-stage impactor at two regional background stations in the eastern China, the Shangdianzi station (SDZ) in the suburb of Beijing and the Lin'An station (LA) in the Yangtze river delta region, both are WMO Global Atmospheric Watch station, which represent the regional background of air pollutions of the two rapid developing economical zone of China, the Yangtze River Delta region (YRD) and Beijing-Tianjin region. The aerosol mass size distributions, ionic compositions, organic and elemental carbon (OC and EC), and elemental components were analyzed. The mass concentrations for TSP (total suspend particle), PM11 (aerodynamic diameter less than 11 μm), and PM2.1 (aerodynamic diameter less than 2.1 μm) at both sites showed obviously different between the winter and summer, with higher mass concentrations measured in the winter time. All seasonal mean mass concentrations of PM2.1 accounted for over 50% of PM11 at both sites. The aerosol mass closure study indicated that the total mass concentration reconstructed from the aerosol chemical composition agreed well with the measured gravimetric mass at the two stations. The fine aerosol particles at the two stations were composed mainly of sulfate and organic matter. In the summer, more than half of the PM2.1 mass was sulfate, suggesting a dominant contribution of secondary aerosol to the fine particles in these two regions. In the winter, the contribution of nitrate to the fine particles increased significantly due to the lower volatile losses under the cold weather. The proportions of soil type components in the PM2.1 showed similar magnitude in the winter and summer at Lin'An station but significant seasonal differences with higher fractions in the winter at Shangdianzi station. On average EC accounted for about 2%-6% of the fine particle mass (PM2.1) at both sites with proportionally lower EC

  13. High-Resolution Electrospray Ionization Mass Spectrometry Analysis of Water- Soluble Organic Aerosols Collected with a Particle into Liquid Sampler

    SciTech Connect

    Bateman, Adam P.; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2010-10-01

    This work demonstrates the utility of a particle-into-liquid sampler (PILS) a technique traditionally used for identification of inorganic ions present in ambient or laboratory aerosols for the analysis of water soluble organic aerosol (OA) using high resolution electrospray ionization mass spectrometry (HR ESI-MS). Secondary organic aerosol (SOA) was produced from 0.5 ppm mixing ratios of limonene and ozone in a 5 m3 Teflon chamber. SOA was collected simultaneously using a traditional filter sampler and a PILS. The filter samples were later extracted with either water or acetonitrile, while the aqueous PILS samples were analyzed directly. In terms of peak intensities, types of detectable compounds, average O:C ratios, and organic mass to organic carbon ratios, the resulting high resolution mass spectra were essentially identical for the PILS and filter based samples. SOA compounds extracted from both filter/acetonitrile extraction and PILS/water extraction accounted for >95% of the total ion current in ESI mass spectra. This similarity was attributed to high solubility of limonene SOA in water. In contrast, significant differences in detected ions and peak abundances were observed for pine needle biomass burning organic aerosol (BBOA) collected with PILS and filter sampling. The water soluble fraction of BBOA is considerably smaller than for SOA, and a number of unique peaks were detectable only by the filter/acetonitrile method. The combination of PILS collection with HR-ESI-MS analysis offers a new approach for molecular analysis of the water-soluble organic fraction in biogenic SOA, aged photochemical smog, and BBOA.

  14. Mass fractionation of the lunar surface by solar wind sputtering

    NASA Technical Reports Server (NTRS)

    Switkowski, Z. E.; Haff, P. K.; Tombrello, T. A.; Burnett, D. S.

    1977-01-01

    An investigation is conducted concerning the mass-fractionation effects produced in connection with the bombardment of the moon by the solar wind. Most of the material ejected by sputtering escapes the moon's gravity, but some returning matter settles back onto the lunar surface. This material, which is somewhat richer in heavier atoms than the starting surface, is incorporated into the heavily radiation-damaged outer surfaces of grains. The investigation indicates that sputtering of the lunar surface by the solar wind will give rise to significant surface heavy atom enrichments if the grain surfaces are allowed to come into sputtering equilibrium.

  15. Mass spectrometry investigation of Titan aerosols analogs formed with traces of aromatic compounds

    NASA Astrophysics Data System (ADS)

    Gautier, Thomas; Trainer, Melissa; Sebree, Joshua; Li, Xiang; Pinnick, Veronica; Getty, Stephanie; Brinckerhoff, Will

    2016-06-01

    The detection of benzene at ppm levels in Titan's atmosphere [1] by Cassini's Ion and Neutral Mass Spectrometer (INMS) supports the idea that aromatic and heteroaromatic reaction pathways may play an important role in Titan's aerosols formation. In laboratory studies it has been shown that these aromatic molecules are easily dissociated by ultraviolet radiation and can therefore contribute significantly to aerosol formation [2] and be used to dope the production of aerosol analogs [3]. In this work we investigate the effect on the aerosol composition and growth pattern of the chemical nature of the aromatic reactant used to produce aerosol. Analysis are performed using Laser Desorption-Time of Flight mass spectrometry (LD-TOF) and Fourier Transform Infrared Spectroscopy (FTIR) Infrared analysis of our samples shows that inclusion of aromatic compounds as trace precursors allows to better fit laboratory data to Titan aerosol spectra observed by Cassini [3,4]. The improvement is especially visible on the far infrared (˜200 cm‑1) bands observed by CIRS [5]. LDMS results show that the aerosol growth patterns depend both on the number of rings and on the nitrogen content of the trace precursor used. We also perform MS/MS analysis on some prominent peaks of aerosol mass spectra. This MS/MS approach allows us to identify some of the key compounds in the aerosol growth processes.

  16. Mass spectrometry investigation of Titan aerosols analogs formed with traces of aromatic compounds

    NASA Astrophysics Data System (ADS)

    Gautier, Thomas; Trainer, Melissa; Sebree, Joshua; Li, Xiang; Pinnick, Veronica; Getty, Stephanie; Brinckerhoff, Will

    2016-06-01

    The detection of benzene at ppm levels in Titan's atmosphere [1] by Cassini's Ion and Neutral Mass Spectrometer (INMS) supports the idea that aromatic and heteroaromatic reaction pathways may play an important role in Titan's aerosols formation. In laboratory studies it has been shown that these aromatic molecules are easily dissociated by ultraviolet radiation and can therefore contribute significantly to aerosol formation [2] and be used to dope the production of aerosol analogs [3]. In this work we investigate the effect on the aerosol composition and growth pattern of the chemical nature of the aromatic reactant used to produce aerosol. Analysis are performed using Laser Desorption-Time of Flight mass spectrometry (LD-TOF) and Fourier Transform Infrared Spectroscopy (FTIR) Infrared analysis of our samples shows that inclusion of aromatic compounds as trace precursors allows to better fit laboratory data to Titan aerosol spectra observed by Cassini [3,4]. The improvement is especially visible on the far infrared (˜200 cm-1) bands observed by CIRS [5]. LDMS results show that the aerosol growth patterns depend both on the number of rings and on the nitrogen content of the trace precursor used. We also perform MS/MS analysis on some prominent peaks of aerosol mass spectra. This MS/MS approach allows us to identify some of the key compounds in the aerosol growth processes.

  17. Reduction in biomass burning aerosol light absorption upon humidification: Roles of inorganically-induced hygroscopicity, particle collapse, and photoacoustic heat and mass transfer

    SciTech Connect

    lewis, Kristen A.; Arnott, W. P.; Moosmuller, H.; Chakrabarti, Raj; Carrico, Christian M.; Kreidenweis, Sonia M.; Day, Derek E.; Malm, William C.; Laskin, Alexander; Jimenez, Jose L.; Ulbrich, Ingrid M.; Huffman, John A.; Onasch, Timothy B.; Trimborn, Achim; Liu, Li; Mishchenko, M.

    2009-11-27

    Smoke particle emissions from the combustion of biomass fuels typical for the western and southeastern United States were studied and compared under high humidity and ambient conditions in the laboratory. The fuels used are Montana ponderosa pine (Pinus ponderosa), southern California chamise (Adenostoma fasciculatum), and Florida saw palmetto (Serenoa repens). Information on the non-refractory chemical composition of biomass burning aerosol from each fuel was obtained with an aerosol mass spectrometer and through estimation of the black carbon concentration from light absorption measurements at 870 nm. Changes in the optical and physical particle properties under high humidity conditions were observed for hygroscopic smoke particles containing substantial inorganic mass fractions that were emitted from combustion of chamise and palmetto fuels. Light scattering cross sections increased under high humidity for these particles, consistent with the hygroscopic growth measured for 100 nm particles in HTDMA measurements. Photoacoustic measurements of aerosol light absorption coefficients reveal a 20% reduction with increasing relative humidity, contrary to the expectation of light absorption enhancement by the liquid coating taken up by hygroscopic particles. This reduction is hypothesized to arise from two mechanisms: 1. Shielding of inner monomers after particle consolidation or collapse with water uptake; 2. The contribution of mass transfer through evaporation and condensation at high relative humidity to the usual heat transfer pathway for energy release by laser heated particles in the photoacoustic measurement of aerosol light absorption. The mass transfer contribution is used to evaluate the fraction of aerosol surface covered with liquid water solution as a function of RH.

  18. Aerosol matrix-assisted laser desorption ionization for liquid chromatography/time-of-flight mass spectrometry

    SciTech Connect

    Murray, K.K.; Lewis, T.M.; Beeson, M.D.; Russell, D.H. )

    1994-05-15

    We report the application of aerosol matrix-assisted laser desorption ionization (MALDI) to liquid chromatography/mass spectrometry (LC/MS). The aerosol MALDI experiment uses aerosol liquid introduction in conjunction with pulsed UV laser ionization to form ions from large biomolecules in solution. Mass analysis is achieved in a time-of-flight mass spectrometer. In the LC/MALDI-MS experiment, the matrix solution is combined with the column effluent in a mixing tee, LC/MALDI-MS is demonstrated for the separation of bradykinin, gramicidin S, and myoglobin. 32 refs., 8 figs., 1 tab.

  19. TWO EXTRASOLAR ASTEROIDS WITH LOW VOLATILE-ELEMENT MASS FRACTIONS

    SciTech Connect

    Jura, M.; Xu, S.; Klein, B.; Zuckerman, B.; Koester, D. E-mail: sxu@astro.ucla.edu E-mail: ben@astro.ucla.edu

    2012-05-01

    Using ultraviolet spectra obtained with the Cosmic Origins Spectrograph on the Hubble Space Telescope, we extend our previous ground-based optical determinations of the composition of the extrasolar asteroids accreted onto two white dwarfs, GD 40 and G241-6. Combining optical and ultraviolet spectra of these stars with He-dominated atmospheres, 13 and 12 polluting elements are confidently detected in GD 40 and G241-6, respectively. For the material accreted onto GD 40, the volatile elements C and S are deficient by more than a factor of 10 and N by at least a factor of 5 compared to their mass fractions in primitive CI chondrites and approach what is inferred for bulk Earth. A similar pattern is found for G241-6 except that S is undepleted. We have also newly detected or placed meaningful upper limits for the amount of Cl, Al, P, Ni, and Cu in the accreted matter. Extending results from optical studies, the mass fractions of refractory elements in the accreted parent bodies are similar to what is measured for bulk Earth and chondrites. Thermal processing, perhaps interior to a snow line, appears to be of central importance in determining the elemental compositions of these particular extrasolar asteroids.

  20. Time-resolved mass concentration, composition and sources of aerosol particles in a metropolitan underground railway station

    NASA Astrophysics Data System (ADS)

    Salma, Imre; Weidinger, Tamás; Maenhaut, Willy

    Aerosol samples were collected using a stacked filter unit (SFU) for PM10-2.0 and PM2.0 size fractions on the platform of a metropolitan underground railway station in downtown Budapest. Temporal variations in the PM10 mass concentration and wind speed and direction were determined with time resolutions of 30 and 4 s using a tapered-element oscillating microbalance (TEOM) and a wind monitor, respectively. Sample analysis involved gravimetry for particulate mass, and particle-induced X-ray emission spectrometry (PIXE) for elemental composition. Diurnal variation of the PM10 mass concentration exhibited two peaks, one at approximately 07:00 h and the other at approximately 17:00 h. The mean±SD PM10 mass concentration for working hours was 155±55 μg m -3. Iron, Mn, Ni, Cu, and Cr concentrations were higher than in outdoor air by factors between 5 and 20, showing substantial enrichment compared to both the average crustal rock composition and the average outdoor aerosol composition. Iron accounted for 40% and 46% of the PM10-2.0 and PM2.0 masses, respectively, and 72% of the PM10 mass was associated with the PM10-2.0 size fraction. The aerosol composition in the metro station (in particular the abundance of the metals mentioned above) is quite different from the average outdoor downtown composition. Mechanical wear and friction of electric conducting rails and bow sliding collectors, ordinary rails and wheels, as well as resuspension, were identified as the primary sources. Possible health implications based on comparison to various limit values and to data available for other underground railways are discussed.

  1. Chemical composition and characteristics of ambient aerosols and rainwater residues during Indian summer monsoon: Insight from aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida N.

    2016-07-01

    Real time composition of non-refractory submicron aerosol (NR-PM1) is measured via Aerosol mass spectrometer (AMS) for the first time during Indian summer monsoon at Kanpur, a polluted urban location located at the heart of Indo Gangetic Plain (IGP). Submicron aerosols are found to be dominated by organics followed by nitrate. Source apportionment of organic aerosols (OA) via positive matrix factorization (PMF) revealed several types of secondary/oxidized and primary organic aerosols. On average, OA are completely dominated by oxidized OA with a very little contribution from biomass burning OA. During rain events, PM1 concentration is decreased almost by 60%, but its composition remains nearly the same. Oxidized OA showed slightly more decrease than primary OAs, probably due to their higher hygroscopicity. The presence of organo nitrates (ON) is also detected in ambient aerosols. Apart from real-time sampling, collected fog and rainwater samples were also analyzed via AMS in offline mode and in the ICP-OES (Inductively coupled plasma - Optical emission spectrometry) for elements. The presence of sea salt, organo nitrates and sulfates has been observed. Rainwater residues are also dominated by organics but their O/C ratios are 15-20% lower than the observed values for ambient OA. Alkali metals such as Ca, Na, K are found to be most abundant in the rainwater followed by Zn. Rainwater residues are also found to be much less oxidized than the aerosols present inside the fog water, indicating presence of less oxidized organics. These findings indicate that rain can act as an effective scavenger of different types of pollutants even for submicron particle range. Rainwater residues also contain organo sulfates which indicate that some portion of the dissolved aerosols has undergone aqueous processing, possibly inside the cloud. Highly oxidized and possibly hygroscopic OA during monsoon period compared to other seasons (winter, post monsoon), indicates that they can act

  2. Secondary Aerosol Formation in the planetary boundary layer observed by aerosol mass spectrometry on a Zeppelin NT

    NASA Astrophysics Data System (ADS)

    Rubach, Florian; Trimborn, Achim; Mentel, Thomas; Wahner, Andreas; Zeppelin Pegasos-Team 2012

    2014-05-01

    The airship Zeppelin NT is an airborne platform capable of flying at low speed throughout the entire planetary boundary layer (PBL). In combination with the high scientific payload of more than 1 ton, the Zeppelin is an ideal platform to study regional processes in the lowest layers of the atmosphere with high spatial resolution. Atmospheric aerosol as a medium long lived tracer substance is of particular interest due to its influence on the global radiation budget. Due its lifetime of up to several days secondaray aerosol at a certain location can result from local production or from transport processes. For aerosol measurements on a Zeppelin, a High-Resolution Time-of-Flight Aerosol Mass spectrometer (DeCarlo et al, 2006) was adapted to the requirements posed by an airborne platform. A weight reduction of over 20 % compared to the commercial instrument was achieved, while space occupation and footprint were each reduced by over 25 %. Within the PEGASOS project, the instrument was part of 10 measurement flight days over the course of seven weeks. Three flights were starting from Rotterdam, NL, seven flights were starting from Ozzano in the Po Valley, IT. Flight patterns included vertical profiles to study the dynamics of the PBL and cross sections through regions of interest to shed light on local production and transport processes. Analysis of data from transects between the Apennin and San Pietro Capofiume in terms of "residence time of air masses in the Po valley" indicates that aerosol nitrate has only local sources while aerosol sulfate is dominated by transport. The organic aerosol component has significant contributions of both processes. The local prodcution yields are commensurable with imultaneously observed precursor concentrations and oxidant levels. The PEGASOS project is funded by the European Commission under the Framework Programme 7 (FP7-ENV-2010-265148). DeCarlo, P.F. et al (2006), Anal. Chem., 78, 8281-8289.

  3. Comparison of methods for the quantification of the different carbon fractions in atmospheric aerosol samples

    NASA Astrophysics Data System (ADS)

    Nunes, Teresa; Mirante, Fátima; Almeida, Elza; Pio, Casimiro

    2010-05-01

    Atmospheric carbon consists of: organic carbon (OC, including various organic compounds), elemental carbon (EC, or black carbon [BC]/soot, a non-volatile/light-absorbing carbon), and a small quantity of carbonate carbon. Thermal/optical methods (TOM) have been widely used for quantifying total carbon (TC), OC, and EC in ambient and source particulate samples. Unfortunately, the different thermal evolution protocols in use can result in a wide elemental carbon-to-total carbon variation. Temperature evolution in thermal carbon analysis is critical to the allocation of carbon fractions. Another critical point in OC and EC quantification by TOM is the interference of carbonate carbon (CC) that could be present in the particulate samples, mainly in the coarse fraction of atmospheric aerosol. One of the methods used to minimize this interference consists on the use of a sample pre-treatment with acid to eliminate CC prior to thermal analysis (Chow et al., 2001; Pio et al., 1994). In Europe, there is currently no standard procedure for determining the carbonaceous aerosol fraction, which implies that data from different laboratories at various sites are of unknown accuracy and cannot be considered comparable. In the framework of the EU-project EUSAAR, a comprehensive study has been carried out to identify the causes of differences in the EC measured using different thermal evolution protocols. From this study an optimised protocol, the EUSAAR-2 protocol, was defined (Cavali et al., 2009). During the last two decades thousands of aerosol samples have been taken over quartz filters at urban, industrial, rural and background sites, and also from plume forest fires and biomass burning in a domestic closed stove. These samples were analysed for OC and EC, by a TOM, similar to that in use in the IMPROVE network (Pio et al., 2007). More recently we reduced the number of steps in thermal evolution protocols, without significant repercussions in the OC/EC quantifications. In order

  4. Real-time analysis of ambient organic aerosols using aerosol flowing atmospheric-pressure afterglow mass spectrometry (AeroFAPA-MS)

    NASA Astrophysics Data System (ADS)

    Brüggemann, Martin; Karu, Einar; Stelzer, Torsten; Hoffmann, Thorsten

    2015-04-01

    Organic aerosol accounts for a major fraction of atmospheric aerosols and has implications on the earth's climate and human health. However, due to the chemical complexity its measurement remains a major challenge for analytical instrumentation.1 Here, we present the development, characterization and application of a new soft ionization technique that allows mass spectrometric real-time detection of organic compounds in ambient aerosols. The aerosol flowing atmospheric-pressure afterglow (AeroFAPA) ion source utilizes a helium glow discharge plasma to produce excited helium species and primary reagent ions. Ionization of the analytes occurs in the afterglow region after thermal desorption and results mainly in intact molecular ions, facilitating the interpretation of the acquired mass spectra. In the past, similar approaches were used to detect pesticides, explosives or illicit drugs on a variety of surfaces.2,3 In contrast, the AeroFAPA source operates 'online' and allows the detection of organic compounds in aerosols without a prior precipitation or sampling step. To our knowledge, this is the first application of an atmospheric-pressure glow discharge ionization technique to ambient aerosol samples. We illustrate that changes in aerosol composition and concentration are detected on the time scale of seconds and in the ng-m-3 range. Additionally, the successful application of AeroFAPA-MS during a field study in a mixed forest region in Central Europe is presented. Several oxidation products of monoterpenes were clearly identified using the possibility to perform tandem MS experiments. The acquired data are in agreement with previous studies and demonstrate that AeroFAPA-MS is a suitable tool for organic aerosol analysis. Furthermore, these results reveal the potential of this technique to enable new insights into aerosol formation, growth and transformation in the atmosphere. References: 1) IPCC, 2013: Summary for Policymakers. In: Climate Change 2013: The

  5. Unraveling the Complexity of Atmospheric Aerosol: Insights from Ultrahigh Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Mazzoleni, Lynn R.; Zhao, Yunzhu; Samburova, Vera; Gannet Hallar, A.; Lowenthal, Douglas

    2016-04-01

    Atmospheric aerosol organic matter (AOM) is a complex mixture of thousands of organic compounds, which may have significant influence on the climate-relevant properties of atmospheric aerosols. An improved understanding of the molecular composition of AOM is needed to evaluate the effect of aerosol composition upon aerosol physical properties. Products of gas, aqueous and particle phase reactions contribute to the aerosol organic mass. Thus, ambient aerosols carry a complex array of AOM components with variable chemical signatures depending upon its origin and aerosol life-cycle processes. In this work, ultrahigh-resolution Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize ambient aerosol AOM collected at the Storm Peak Laboratory (3210 m a.s.l.) near Steamboat Springs, CO. Thousands of molecular formulas were assigned in the mass range of m/z 100-800 after negative-ion electrospray ionization. Using multivariate statistical analysis, correlations between the site meteorological conditions and specific molecular compositions were identified. For example, days with strong UV radiation and high temperature were found to contain large numbers of biogenic SOA molecular formulas. Similarly, days with high relative humidity and high sulfate concentrations were found to contain many sulfur-containing compounds, suggesting their aqueous phase formation.

  6. Aerosol speciation and mass prediction from toluene oxidation under high NO x conditions

    NASA Astrophysics Data System (ADS)

    Kelly, Janya L.; Michelangeli, Diane V.; Makar, Paul A.; Hastie, Donald R.; Mozurkewich, Michael; Auld, Janeen

    2010-01-01

    A kinetically based gas-particle partitioning box model is used to highlight the importance of parameter representation in the prediction of secondary organic aerosol (SOA) formation following the photo-oxidation of toluene. The model is initialized using experimental data from York University's indoor smog chamber and provides a prediction of the total aerosol yield and speciation. A series of model sensitivity experiments were performed to study the aerosol speciation and mass prediction under high NO x conditions (VOC/NO x = 0.2). Sensitivity experiments indicate vapour pressure estimation to be a large area of weakness in predicting aerosol mass, creating an average total error range of 70 μg m -3 (range of 5-145 μg m -3), using two different estimation methods. Aerosol speciation proved relatively insensitive to changes in vapour pressure. One species, 3-methyl-6-nitro-catechol, dominated the aerosol phase regardless of the vapour pressure parameterization used and comprised 73-88% of the aerosol by mass. The dominance is associated with the large concentration of 3-methyl-6-nitro-catechol in the gas-phase. The high NO x initial conditions of this study suggests that the predominance of 3-methyl-6-nitro-catechol likely results from the cresol-forming branch in the Master Chemical Mechanism taking a significant role in secondary organic aerosol formation under high NO x conditions. Further research into the yields and speciation leading to this reaction product is recommended.

  7. Fractal morphology, imaging and mass spectrometry of single aerosol particles in flight (CXIDB ID 16)

    DOE Data Explorer

    Loh, N. Duane

    2012-06-20

    This deposition includes the aerosol diffraction images used for phasing, fractal morphology, and time-of-flight mass spectrometry. Files in this deposition are ordered in subdirectories that reflect the specifics.

  8. Intercomparison of elemental concentrations in total and size-fractionated aerosol samples collected during the mace head experiment, April 1991

    NASA Astrophysics Data System (ADS)

    François, Filip; Maenhaut, Willy; Colin, Jean-Louis; Losno, Remi; Schulz, Michael; Stahlschmidt, Thomas; Spokes, Lucinda; Jickells, Timothy

    During an intercomparison field experiment, organized at the Atlantic coast station of Mace Head, Ireland, in April 1991, aerosol samples were collected by four research groups. A variety of samplers was used, combining both high- and low-volume devices, with different types of collection substrates: Hi-Vol Whatman 41 filter holders, single Nuclepore filters and stacked filter units, as well as PIXE cascade impactors. The samples were analyzed by each participating group, using in-house analytical techniques and procedures. The intercomparison of the daily concentrations for 15 elements, measured by two or more participants, revealed a good agreement for the low-volume samplers for the majority of the elements, but also indicated some specific analytical problems, owing to the very low concentrations of the non-sea-salt elements at the sampling site. With the Hi-Vol Whatman 41 filter sampler, on the other hand, much higher results were obtained in particular for the sea-salt and crustal elements. The discrepancy was dependent upon the wind speed and was attributed to a higher collection efficiency of the Hi-Vol sampler for the very coarse particles, as compared to the low-volume devices under high wind speed conditions. The elemental mass size distribution, as derived from parallel cascade impactor samplings by two groups, showed discrepancies in the submicrometer aerosol fraction, which were tentatively attributed to differences in stage cut-off diameters and/or to bounce-off or splintering effects on the quartz impactor slides used by one of the groups. However, the atmospheric concentrations (sums over all stages) were rather similar in the parallel impactor samples and were only slightly lower than those derived from stacked filter unit samples taken in parallel.

  9. Evaluation of Aerosol Mixing State Classes in the GISS Modele-matrix Climate Model Using Single-particle Mass Spectrometry Measurements

    NASA Technical Reports Server (NTRS)

    Bauer, Susanne E.; Ault, Andrew; Prather, Kimberly A.

    2013-01-01

    Aerosol particles in the atmosphere are composed of multiple chemical species. The aerosol mixing state, which describes how chemical species are mixed at the single-particle level, provides critical information on microphysical characteristics that determine the interaction of aerosols with the climate system. The evaluation of mixing state has become the next challenge. This study uses aerosol time-of-flight mass spectrometry (ATOFMS) data and compares the results to those of the Goddard Institute for Space Studies modelE-MATRIX (Multiconfiguration Aerosol TRacker of mIXing state) model, a global climate model that includes a detailed aerosol microphysical scheme. We use data from field campaigns that examine a variety of air mass regimens (urban, rural, and maritime). At all locations, polluted areas in California (Riverside, La Jolla, and Long Beach), a remote location in the Sierra Nevada Mountains (Sugar Pine) and observations from Jeju (South Korea), the majority of aerosol species are internally mixed. Coarse aerosol particles, those above 1 micron, are typically aged, such as coated dust or reacted sea-salt particles. Particles below 1 micron contain large fractions of organic material, internally-mixed with sulfate and black carbon, and few external mixtures. We conclude that observations taken over multiple weeks characterize typical air mass types at a given location well; however, due to the instrumentation, we could not evaluate mass budgets. These results represent the first detailed comparison of single-particle mixing states in a global climate model with real-time single-particle mass spectrometry data, an important step in improving the representation of mixing state in global climate models.

  10. Evaluation of aerosol mixing state classes in the GISS modelE-MATRIX climate model using single-particle mass spectrometry measurements

    NASA Astrophysics Data System (ADS)

    Bauer, Susanne E.; Ault, Andrew; Prather, Kimberly A.

    2013-09-01

    Aerosol particles in the atmosphere are composed of multiple chemical species. The aerosol mixing state, which describes how chemical species are mixed at the single-particle level, provides critical information on microphysical characteristics that determine the interaction of aerosols with the climate system. The evaluation of mixing state has become the next challenge. This study uses aerosol time-of-flight mass spectrometry (ATOFMS) data and compares the results to those of the Goddard Institute for Space Studies modelE-MATRIX (Multiconfiguration Aerosol TRacker of mIXing state) model, a global climate model that includes a detailed aerosol microphysical scheme. We use data from field campaigns that examine a variety of air mass regimens (urban, rural, and maritime). At all locations, polluted areas in California (Riverside, La Jolla, and Long Beach), a remote location in the Sierra Nevada Mountains (Sugar Pine) and observations from Jeju (South Korea), the majority of aerosol species are internally mixed. Coarse aerosol particles, those above 1 µm, are typically aged, such as coated dust or reacted sea-salt particles. Particles below 1 µm contain large fractions of organic material, internally mixed with sulfate and black carbon, and few external mixtures. We conclude that observations taken over multiple weeks characterize typical air mass types at a given location well; however, due to the instrumentation, we could not evaluate mass budgets. These results represent the first detailed comparison of single-particle mixing states in a global climate model with real-time single-particle mass spectrometry data, an important step in improving the representation of mixing state in global climate models.

  11. Variability of Marine Aerosol Fine-Mode Fraction and Estimates of Anthropogenic Aerosol Component Over Cloud-Free Oceans from the Moderate Resolution Imaging Spectroradiometer (MODIS)

    NASA Technical Reports Server (NTRS)

    Yu, Hongbin; Chin, Mian; Remer, Lorraine A.; Kleidman, Richard G.; Bellouin, Nicolas; Bian, Huisheng; Diehl, Thomas

    2009-01-01

    In this study, we examine seasonal and geographical variability of marine aerosol fine-mode fraction (f(sub m)) and its impacts on deriving the anthropogenic component of aerosol optical depth (tau(sub a)) and direct radiative forcing from multispectral satellite measurements. A proxy of f(sub m), empirically derived from the Moderate Resolution Imaging Spectroradiometer (MODIS) Collection 5 data, shows large seasonal and geographical variations that are consistent with the Goddard Chemistry Aerosol Radiation Transport (GOCART) and Global Modeling Initiative (GMI) model simulations. The so-derived seasonally and spatially varying f(sub m) is then implemented into a method of estimating tau(sub a) and direct radiative forcing from the MODIS measurements. It is found that the use of a constant value for fm as in previous studies would have overestimated Ta by about 20% over global ocean, with the overestimation up to 45% in some regions and seasons. The 7-year (2001-2007) global ocean average tau(sub a) is 0.035, with yearly average ranging from 0.031 to 0.039. Future improvement in measurements is needed to better separate anthropogenic aerosol from natural ones and to narrow down the wide range of aerosol direct radiative forcing.

  12. Dynamical Models to Infer the Core Mass Fraction of Venus

    NASA Astrophysics Data System (ADS)

    Quintana, Elisa V.; Barclay, Thomas

    2016-10-01

    The uncompressed density of Venus is just a few percent lower than Earth's, however the nature of the interior core structure of Venus remains unclear. Employing state-of-the-art dynamical formation models that allow both accretion and collisional fragmentation, we perform hundreds of simulations of terrestrial planet growth around the Sun in the presence of the giant planets. For both Earth and Venus analogs, we quantify the iron-silicate ratios, water/volatile abundances and specific impact energies of all collisions that lead to their formation. Preliminary results suggest that the distributions of core mass fraction and water content are comparable among the Earth and Venus analogs, suggesting that Earth and Venus may indeed have formed with similar structures and compositions.

  13. The relevance of aerosol optical depth to cumulus fraction changes: a five-year climatology at the ACRF SGP site

    NASA Astrophysics Data System (ADS)

    Kassianov, E. I.; Berg, L. K.; Flynn, C.; McFarlane, S.

    2007-08-01

    The objective of this study is to investigate, by observational means, the magnitude and sign of the actively discussed relationship between cloud fraction N and aerosol optical depth τa. Collocated and coincident ground-based measurements and Terra/Aqua satellite observations at the Atmospheric Radiation Measurement (ARM) Climate Research Facility (ACRF) Southern Great Plains (SGP) site form the basis of this study. The N-τa relationship occurred in a specific 5-year dataset of fair-weather cumulus (FWC) clouds and mostly non-absorbing aerosols. To reduce possible contamination of the aerosols on the cloud properties estimation (and vice versa), we use independent datasets of τa and N obtained from the Multi-filter Rotating Shadowband Radiometer (MFRSR) measurements and from the ARM Active Remotely Sensed Clouds Locations (ARSCL) value-added product, respectively. Optical depth of the FWC clouds τcld and effective radius of cloud droplets re are obtained from the MODerate resolution Imaging Spectroradiometer (MODIS) data. We found that relationships between cloud properties (N,τcld, re) and aerosol optical depth are time-dependent (morning versus afternoon). Observed time-dependent changes of cloud properties, associated with aerosol loading, control the variability of surface radiative fluxes. In comparison with pristine clouds, the polluted clouds are more transparent in the afternoon due to smaller cloud fraction, smaller optical depth and larger droplets. As a result, the corresponding correlation between the surface radiative flux and τa is positive (warming effect of aerosol). Also we found that relationship between cloud fraction and aerosol optical depth is cloud size dependent. The cloud fraction of large clouds (larger than 1 km) is relatively insensitive to the aerosol amount. In contrast, cloud fraction of small clouds (smaller than 1 km) is strongly positively correlated with τa. This suggests that an ensemble of polluted clouds tends to be

  14. Chemical characterization of emissions from vegetable oil processing and their contribution to aerosol mass using the organic molecular markers approach.

    PubMed

    Kavouras, I G; Stratigakis, N; Stephanou, E G

    2001-04-01

    The organic fraction of aerosol emitted from a vegetable oil processing plant was studied to investigate the contribution of emissions to ambient particles in the surrounding area. Solvent-soluble particulate organic compounds emitted from the plant accounted for 10% of total suspended particles. This percentage was lower in the receptor sites (less than 6% of total aerosol mass). Nonpolar, moderate polar, polar, and acidic compounds were detected in both emitted and ambient aerosol samples. The processing and combustion of olive pits yielded a source with strong biogenic characteristics, such as the high values of the carbon preference index (CPI) for all compound classes. Polycyclic aromatic hydrocarbons (PAHs) detected in emissions were associated with both olive pits and diesel combustion. The chromatographic profile of dimethylphenanthrenes (DMPs) was characteristic of olive pit combustion. Organic aerosols collected in two receptor sites provided a different pattern. The significant contribution of vehicular emissions was identified by CPI values (approximately 1) of n-alkanes and the presence of the unresolved complex mixture (UCM). In addition, PAH concentration diagnostic ratios indicated that emissions from catalyst and noncatalyst automobiles and heavy trucks were significant. The strong even-to-odd predominance of n-alkanols, n-alkanoic acids, and their salts indicated the contribution of a source with biogenic characteristics. However, the profile of DMPs at receptor sites was similar to that observed for diesel particulates. These differences indicated that the contribution of vegetable oil processing emissions to the atmosphere was negligible.

  15. Anthropogenic sources of aerosol particles in a football stadium: Real-time characterization of emissions from cigarette smoking, cooking, hand flares, and color smoke bombs by high-resolution aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Faber, Peter; Drewnick, Frank; Veres, Patrick R.; Williams, Jonathan; Borrmann, Stephan

    2013-10-01

    Aerosol particles from several anthropogenic sources associated with football stadia including cooking, cigarette smoking, burning of color smoke bombs and hand flares were analyzed by high-resolution aerosol mass spectrometry. The physical and chemical characteristics of these different aerosols, in particular the organic fraction, were explored in laboratory studies to obtain robust references. These data were compared with field campaign results from a Bundesliga (German football league) match in the Coface Arena (Mainz, Germany) on 20th April 2012. The field measurement revealed a strongly elevated mass concentration of organic aerosols (OA) compared to background levels showing a temporal structure clearly related to the match. PMF analysis established that during the football match event cigarette smoke was the predominant component of submicron organic aerosol (67% of total OA). Cooking emissions from food outlets within the stadium correlated well with the sales figures of the catering stations and were also found to be of relevance (24% of total OA) especially in the period before kickoff. Pyrotechnics were not observed during this football match and no signatures of these sources were found in the mass spectra from the stadium measurements. All species that were elevated during the football match returned to their initial background levels within one hour after the match had finished. This demonstrates a good ventilation capacity of the open-topped Coface Arena.

  16. Characterization of particulate matter emissions from on-road gasoline and diesel vehicles using a soot particle aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Dallmann, T. R.; Onasch, T. B.; Kirchstetter, T. W.; Worton, D. R.; Fortner, E. C.; Herndon, S. C.; Wood, E. C.; Franklin, J. P.; Worsnop, D. R.; Goldstein, A. H.; Harley, R. A.

    2014-07-01

    Particulate matter (PM) emissions were measured in July 2010 from on-road motor vehicles driving through a highway tunnel in the San Francisco Bay area. A soot particle aerosol mass spectrometer (SP-AMS) was used to measure the chemical composition of PM emitted by gasoline and diesel vehicles at high time resolution. Organic aerosol (OA) and black carbon (BC) concentrations were measured during various time periods that had different levels of diesel influence, as well as directly in the exhaust plumes of individual heavy-duty (HD) diesel trucks. BC emission factor distributions for HD trucks were more skewed than OA distributions (N = 293), with the highest 10% of trucks accounting for 56 and 42% of total measured BC and OA emissions, respectively. OA mass spectra measured for HD truck exhaust plumes show cycloalkanes are predominate in exhaust OA emissions relative to saturated alkanes (i.e., normal and iso-paraffins), suggesting that lubricating oil rather than fuel is the dominant source of primary organic aerosol (POA) emissions in diesel vehicle exhaust. This finding is supported by the detection of trace elements such as zinc and phosphorus in the exhaust plumes of individual trucks. Trace elements were emitted relative to total OA at levels that are consistent with typical weight fractions of commonly used additives present in lubricating oil. A comparison of measured OA and BC mass spectra across various sampling periods revealed a high degree of similarity in OA and BC emitted by gasoline and diesel engines. This finding indicates a large fraction of OA in gasoline exhaust is lubricant-derived as well. The similarity in OA and BC mass spectra for gasoline and diesel engine exhaust is likely to confound ambient source apportionment efforts to determine contributions to air pollution from these two important sources.

  17. Effect of Vaporizer Temperature on Ambient Non-Refractory Submicron Aerosol Composition and Mass Spectra Measured by the Aerosol Mass Spectrometer

    EPA Science Inventory

    Aerodyne Aerosol Mass Spectrometers (AMS) are routinely operated with a constant vaporizer temperature (Tvap) of 600oC in order to facilitate quantitative detection of non-refractory submicron (NR-PM1) species. By analogy with other thermal desorption instrument...

  18. Reporting and measurement of mass-dependent and mass-independent fractionation of mercury isotopes

    NASA Astrophysics Data System (ADS)

    Bergquist, B. A.; Blum, J. D.

    2007-12-01

    Hg isotope analysis by MC-ICP-MS is an important new approach for fingerprinting Hg sources and monitoring Hg redox reactions and bioaccumulation, especially with the recent discovery of mass independent Hg isotope fractionation. Unfortunately research groups have adopted different standards, definitions of delta values, and methods of isotopic measurement. We suggest that a single standard, NIST SRM 3133, be adopted for reporting the isotopic variability of Hg isotopes. Isotope ratios should be determined by sample-standard bracketing (SSB) during analysis and reported as permil (‰) deviation from SRM 3133. For the highest precision and accuracy, a Tl internal standard along with SSB should be used to correct instrumental mass bias. Measurement routines should also include on-peak zero corrections and matching of concentration and matrix between the samples and bracketing standard. For samples that display mass-dependent fractionation (MDF), only one delta value needs to be reported (δ202/198Hg). Mass-independent fractionation (MIF) (Jackson et al., 2006; Bergquist et al., 2006; Bergquist and Blum, submitted) requires additional nomenclature, and we suggest reporting MIF as the deviation in isotope ratios from the theoretical mass dependent kinetic isotope fractionation (Δxxx/198Hg)¬. External reproducibility should be monitored by analysis of secondary standards. For studies of MDF, we use an in-house secondary standard solution made from metallic Hg mined from Almaden Spain and obtain a δ202Hg of -0.55 ±0.06‰ (2SD). For studies of MIF, we use NRCC CRM DORM-2 (dogfish muscle) and obtain a mean value of δ202Hg of +0.19 ±0.13‰ (2SD), Δ201Hg of +0.89 ±0.07‰ (2SD) , and Δ199Hg of +1.07 ±0.08‰ (2SD).

  19. Seasonality of new particle formation in Vienna, Austria - Influence of air mass origin and aerosol chemical composition

    NASA Astrophysics Data System (ADS)

    Wonaschütz, Anna; Demattio, Anselm; Wagner, Robert; Burkart, Julia; Zíková, Naděžda; Vodička, Petr; Ludwig, Wolfgang; Steiner, Gerhard; Schwarz, Jaroslav; Hitzenberger, Regina

    2015-10-01

    The impact of air mass origin and season on aerosol chemical composition and new particle formation and growth events (NPF events) in Vienna, Austria, is investigated using impactor samples from short-term campaigns and two long-term number size distribution datasets. The results suggest that air mass origin is most important for bulk PM concentrations, chemical composition of the coarse fraction (>1.5 μm) and the mass size distribution, and less important for chemical composition of the fine fraction (<1.5 μm). Continental air masses (crustal elements) were distinguished from air masses of marine origin (traces of sea salt). NPF events were most frequent in summer (22% of measurement days), and least frequent in winter (3% of measurement days). They were associated with above-average solar radiation and ozone concentrations, but were largely independent of PM2.5. Air mass origin was a secondary influence on NPF, largely through its association with meteorological conditions. Neither a strong dependence on the PM2.5 loading of the air masses, nor indications of a source area for NPF precursors outside the city were found.

  20. Levels and Speciation of Platinum in Size-Fractionated Atmospheric Aerosol in Urban and Rural Sites across Europe

    NASA Astrophysics Data System (ADS)

    Shafer, Martin; Antkiewicz, Dagmara; Overdier, Joel; Schauer, James

    2016-04-01

    In this study we characterized the levels and speciation of platinum in a unique set of size-resolved atmospheric aerosol (PM) samples obtained from urban environments across Europe. From April-July 2012 we collected PM from roadside canyon, roadside motorway, and background urban sites in each of six European cities (Amsterdam, Frankfurt, London, Milan, Stockholm, and Thessaloniki). A Hi-Vol sampler was used to collect PM in three size classes (>PM7, PM7-PM3, PM3) and characterized for total platinum, soluble platinum (in a suite of physiologically relevant fluids - lung fluid (ALF), Gambles saline, 0.07M HCl, and MQ) and speciated forms (colloidal and anionic) within the soluble fractions. In addition we measured 50 other elements by SF-ICPMS, soluble ions by IC, and soluble organic carbon in the PM. Order-of-magnitude differences in air concentrations of total platinum were observed between urban sites, ranging from 4 to over 45 pg/m3; with a median level of 6 pg/m3. When platinum concentrations are normalized to PM mass the cross Europe and site-to-site variability was substantially reduced - a 3-fold variation from 200 to 600 ng/g was observed. Roadside canyon sites in London, Stockholm and Thessaloniki exhibited the highest concentrations; however levels at urban background sites were remarkably similar across the cities. Relatively consistent and low concentrations (1 to 2 pg/m3) of total platinum were observed at rural background sites across Europe. The contribution of coarse particles (>7 micron and 7-3 micron) to air concentrations of total platinum was very significant (>35% at nearly all sites). Soluble platinum fractions ranged from 2 to 6% (MQ to HCl) in rural background sites to 5 to 20% (MQ to HCl) in roadway canyon sites in London and Thessaloniki; with the extractable platinum fractions a strong function of pH. With the exception of urban canyon sites in London and Thessaloniki, soluble platinum concentrations in the fine aerosol (PM3) were all

  1. Progress Toward a Global, EOS-Era Aerosol Air Mass Type Climatology

    NASA Technical Reports Server (NTRS)

    Kahn, Ralph A.

    2012-01-01

    The MISR and MODIS instruments aboard the NASA Earth Observing System's Terra Satellite have been collecting data containing information about the state of Earth's atmosphere and surface for over eleven years. Data from these instruments have been used to develop a global, monthly climatology of aerosol amount that is widely used as a constraint on climate models, including those used for the 2007 IPCC assessment report. The next frontier in assessing aerosol radiative forcing of climate is aerosol type, and in particular, the absorption properties of major aerosol air masses. This presentation will focus on the prospects for constraining aerosol type globally, and the steps we are taking to apply a combination of satellite and suborbital data to this challenge.

  2. High-Resolution Mass Spectroscopic Analysis of Secondary Organic Aerosol Generated by Ozonolysis of Isoprene

    SciTech Connect

    Nguyen, Tran B; Bateman, Adam P; Bones, David L; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2010-02-01

    The chemical composition of secondary organic aerosol (SOA) generated from the ozonolysis of isoprene (C5H8) in the presence of an OH scavenger was examined using high-resolution electrospray ionization mass spectrometry (ESI-MS). The chemical composition of SOA is complex, with more than 1000 assigned peaks observed in the positive and negative ion mode spectra. Only a small fraction of peaks corresponds to known products of isoprene oxidation, such as pyruvic acid, glycolic acid, methylglyoxal, etc. The absolute majority of the detected peaks correspond to highly oxidized oligomeric constituents of SOA, with an average O:C molar ratio of ~0.6. The corresponding organic mass (OM) to organic oxygen (OO) ratio is OM/OO ~2.4. Approximately 8% of oxygen atoms in SOA are in the form of peroxides as quantified with an iodide test. Double bond equivalency (DBE) factors, representing the sum of all double bonds and rings, increase by 1 for every 2-3 additional carbon atoms in the molecule. The prevalent oligomer building blocks are therefore carbonyls or carboxylic acids with a C2-C3 skeleton. Kendrick analysis suggests that simple aldehydes, specifically formaldehyde, acetaldehyde, and methylglyoxal can serve as monomeric building blocks in the observed oligomers. The large number of reactive functional groups, especially organic peroxides and carbonyls, suggests that isoprene/O3 SOA should be prone to chemical and photochemical aging.

  3. Criteria for significance of simultaneous presence of both condensible vapors and aerosol particles on mass transfer (deposition) rates

    NASA Technical Reports Server (NTRS)

    Gokoglu, S. A.

    1986-01-01

    The simultaneous presence of aerosol particles and condensible vapors in a saturated boundary layer which may affect deposition rates to subcooled surfaces because of vapor-particle interactions is discussed. Scavenging of condensible vapors by aerosol particles may lead to increased particle size and decreased vapor mass fraction, which alters both vapor and particle deposition rates. Particles, if sufficiently concentrated, may also coagulate. Criteria are provided to assess the significance of such phenomena when particles are already present in the mainstream and are not created inside the boundary layer via homogeneous nucleation. It is determined that there is direct proportionality with: (1) the mass concentration of both condensible vapors and aerosol particles; and (2) the square of the boundary layer thickness to particle diameter ratio (delta d sub p) square. Inverse proportionality was found for mainstream to surface temperature difference if thermophoresis dominates particle transport. It is concluded that the square of the boundary layer thickness to particle diameter ratio is the most critical factor to consider in deciding when to neglect vapor-particle interactions.

  4. Identification of aerosol types over an urban site based on air-mass trajectory classification

    NASA Astrophysics Data System (ADS)

    Pawar, G. V.; Devara, P. C. S.; Aher, G. R.

    2015-10-01

    Columnar aerosol properties retrieved from MICROTOPS II Sun Photometer measurements during 2010-2013 over Pune (18°32‧N; 73°49‧E, 559 m amsl), a tropical urban station in India, are analyzed to identify aerosol types in the atmospheric column. Identification/classification is carried out on the basis of dominant airflow patterns, and the method of discrimination of aerosol types on the basis of relation between aerosol optical depth (AOD500 nm) and Ångström exponent (AE, α). Five potential advection pathways viz., NW/N, SW/S, N, SE/E and L have been identified over the observing site by employing the NOAA-HYSPLIT air mass back trajectory analysis. Based on AE against AOD500 nm scatter plot and advection pathways followed five major aerosol types viz., continental average (CA), marine continental average (MCA), urban/industrial and biomass burning (UB), desert dust (DD) and indeterminate or mixed type (MT) have been identified. In winter, sector SE/E, a representative of air masses traversed over Bay of Bengal and Eastern continental Indian region has relatively small AOD (τpλ = 0.43 ± 0.13) and high AE (α = 1.19 ± 0.15). These values imply the presence of accumulation/sub-micron size anthropogenic aerosols. During pre-monsoon, aerosols from the NW/N sector have high AOD (τpλ = 0.61 ± 0.21), and low AE (α = 0.54 ± 0.14) indicating an increase in the loading of coarse-mode particles over Pune. Dominance of UB type in winter season for all the years (i.e. 2010-2013) may be attributed to both local/transported aerosols. During pre-monsoon seasons, MT is the dominant aerosol type followed by UB and DD, while the background aerosols are insignificant.

  5. Mass-analysis of Charged Aerosol Particles in a PMSE/NLC Layer by a Rocket-borne Spectrometer

    NASA Astrophysics Data System (ADS)

    Robertson, Scott; Knappmiller, Scott; Horanyi, Mihaly; Sternovsky, Zoltan; Baumgarten, Gerd; Latteck, Ralph; Rapp, Markus; Holzworth, Robert; Shimogawa, Michael; Gumbel, Jorg; Megner, Ms Linda; Friedrich, Martin

    Two "MASS" rockets (Mesospheric Aerosol Sampling Spectrometer) were launched from the Andoya Rocket Range (Norway) the first week of August 2007. The payloads carried an electrostatic mass analyzer for the charged fraction of the aerosol particles, electric field booms, a photometer for cloud brightness, and Faraday rotation antennas for electron density. Aerosol particles with different ranges of charge-to-mass ratio were collected within the instrument housing on two sets of four biased collector plates, with one set for positive particles and one set for negative particles. The first rocket was launched into PMSE and NLC on 3 August. The sun was 4 degrees below the horizon and NLC were seen in the previous hour at 83 km by the ALOMAR RMR lidar. NLC were detected at the same altitude by rocket-borne photometer measurements. The charged aerosol data shows the density of negative particles with radius greater than 3 nm rising sharply at 83 km and continuing to 89 km, collocated with PMSE detected by the ALWIN radar. Particles with 1-2 nm radii with both signs of charge and particles with less than 1 nm radius charged positively were detected at 86-88 km. The occurrence of the positive particles in the smallest size range in the region of lowest temperature suggests that their origin is nucleation and growth on ions. Initial charge-density estimates are several thousands per cubic centimeter for each of these size ranges. The second launch was 6 August into PMSE without NLC. The 1-2 nm particles were seen from 85.4 to 87.4 km, again with both signs of charge. Larger sizes were nearly absent.

  6. Evolution of organic aerosol mass spectra upon heating: implications for OA phase and partitioning behavior

    SciTech Connect

    UC Davis; Cappa, Christopher D.; Wilson, Kevin R.

    2010-10-28

    Vacuum Ultraviolet (VUV) photoionization mass spectrometry has been used to measure the evolution of chemical composition for two distinct organic aerosol types as they are passed through a thermodenuder at different temperatures. The two organic aerosol types considered are primary lubricating oil (LO) aerosol and secondary aerosol from the alpha-pinene + O3 reaction (alphaP). The evolution of the VUV mass spectra for the two aerosol types with temperature are observed to differ dramatically. For LO particles, the spectra exhibit distinct changes with temperature in which the lower m/z peaks, corresponding to compounds with higher vapor pressures, disappear more rapidly than the high m/z peaks. In contrast, the alphaP aerosol spectrum is essentially unchanged by temperature even though the particles experience significant mass loss due to evaporation. The variations in the LO spectra are found to be quantitatively in agreement with expectations from absorptive partitioning theory whereas the alphaP spectra suggest that the evaporation of alphaP derived aerosol appears to not be governed by partitioning theory. We postulate that this difference arises from the alphaP particles existing as in a glassy state instead of having the expected liquid-like behavior. To reconcile these observations with decades of aerosol growth measurements, which indicate that OA formation is described by equilibrium partitioning, we present a conceptual model wherein the secondary OA is formed and then rapidly converted from an absorbing form to a non-absorbing form. The results suggest that although OA growth may be describable by equilibrium partitioning theory, the properties of organic aerosol once formed may differ significantly from the properties determined in the equilibrium framework.

  7. Fast Airborne Aerosol Size and Chemistry Measurements with the High Resolution Aerosol Mass Spectrometer during the MILAGRO Campaign

    NASA Technical Reports Server (NTRS)

    DeCarlo, P. F.; Dunlea, E. J.; Kimmel, J. R.; Aiken, A. C.; Sueper, D.; Crounse, J.; Wennberg, P. O.; Emmons, L.; Shinozuka, Y.; Clarke, A.; Zhou, J.; Tomlinson, J.; Collins,D. R.; Knapp, D.; Weinheimer, A. J.; Montzka,D. D.; Campos,T.; Jimenez, J. L.

    2007-01-01

    The concentration, size, and composition of non-refractory submicron aerosol (NR-PM(sub l)) was measured over Mexico City and central Mexico with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign. This was the first aircraft deployment of the HR-ToF-AMS. During the campaign the instrument performed very well, and provided 12 s data. The aerosol mass from the AMS correlates strongly with other aerosol measurements on board the aircraft. Organic aerosol (OA) species dominate the NR-PM(sub l) mass. OA correlates strongly with CO and HCN indicating that pollution (mostly secondary OA, SOA) and biomass burning (BB) are the main OA sources. The OA to CO ratio indicates a typical value for aged air of around 80 microg/cubic m (STP) ppm(exp -1). This is within the range observed in outflow from the Northeastern US, which could be due to a compensating effect between higher BB but lower biogenic VOC emissions during this study. The O/C atomic ratio for OA is calculated from the HR mass spectra and shows a clear increase with photochemical age, as SOA forms rapidly and quickly overwhelms primary urban OA, consistent with Volkamer et al. (2006) and Kleinman et al. (2008). The stability of the OA/CO while O/C increases with photochemical age implies a net loss of carbon from the OA. BB OA is marked by signals at m/z 60 and 73, and also by a signal enhancement at large m/z indicative of larger molecules or more resistance to fragmentation. The main inorganic components show different spatial patterns and size distributions. Sulfate is regional in nature with clear volcanic and petrochemical/power plant sources, while the urban area is not a major regional source for this species. Nitrate is enhanced significantly in the urban area and immediate outflow, and is strongly correlated with CO indicating a strong urban source. The importance of nitrate decreases with distance from the city

  8. Single Particle Fluorescence & Mass Spectrometry for the Detection of Biological Aerosols

    SciTech Connect

    Coffee, K; Riot, V; Woods, B; Steele, P; Gard, E E

    2005-04-25

    Biological Aerosol Mass Spectrometry (BAMS) is an emerging technique for the detection of biological aerosols, which is being developed at Lawrence Livermore National Laboratory. The current system uses several orthogonal analytical methods to improve system selectivity, sensitivity and speed in order to maximize its utility as a biological aerosol detection system with extremely low probability of false alarm and high probability of detection. Our approach is to pre-select particles of interest by size and fluorescence prior to mass spectral analysis. The ability to distinguish biological aerosols from background and to discriminate bacterial spores, vegetative cells, viruses and toxins from one another will be shown. Data from particle standards of known chemical composition will be discussed. Analysis of ambient particles will also be presented.

  9. Isotopic mass independent signature of black crusts: a proxy for atmospheric aerosols formation in the Paris area (France).

    NASA Astrophysics Data System (ADS)

    Genot, Isabelle; Martin, Erwan; Yang, David Au; De Rafelis, Marc; Cartigny, Pierre; Wing, Boswell; Le Gendre, Erwann; Bekki, Slimane

    2016-04-01

    In view of the negative forcing of the sulfate aerosols on climate, a more accurate understanding of the formation of these particles is crucial. Indeed, despite the knowledge of their effects, uncertainties remain regarding the formation of sulfate aerosols, particularly the oxidation processes of S-bearing gases. Since the discovery of oxygen and sulfur mass independent fractionation (O- and S-MIF) processes on Earth, the sulfate isotopic composition became essential to investigate the atmospheric composition evolution and its consequences on the climate and the biosphere. Large amount of S-bearing compounds (SO2 mainly) is released into the atmosphere by anthropogenic and natural sources. Their oxidation in the atmosphere generates sulfate aerosols, H2SO4, which precipitate on the earth surface mainly as acid rain. One consequence of this precipitation is the formation of black crust on buildings made of carbonate stones. Indeed the chemical alteration of CaCO3 by H2SO4 leads to gypsum (CaSO4·2H2O) concretions on building walls. Associated to other particles, gypsum forms black-crusts. Therefore, black crusts acts as 'sulfate aerosol traps', meaning that their isotopic composition reveals the composition and thus the source and formation processes of sulfate aerosols in the atmosphere in a specific region. In this study we collected 37 black crusts on a 300km NW-SE profile centered on Paris (France). In our samples, sulfate represent 40wt.% and other particles 60wt.% of the black crusts. After sulfate extraction from each samples we measured their O- and S-isotopes composition. Variations of about 10‰ in δ18O and δ34S are observed and both O-MIF (Δ17O from 0 to 1.4‰) and S-MIF (Δ33S from 0 to -0.3‰) compositions have been measured. In regards to these compositions we can discuss the source and formation (oxidation pathways) of the sulfate aerosols in troposphere above the Paris region that covers urban, rural and coastal environments. Furthermore

  10. Calculating the mass fraction of primordial black holes

    SciTech Connect

    Young, Sam; Byrnes, Christian T.; Sasaki, Misao E-mail: ctb22@sussex.ac.uk

    2014-07-01

    We reinspect the calculation for the mass fraction of primordial black holes (PBHs) which are formed from primordial perturbations, finding that performing the calculation using the comoving curvature perturbation R{sub c} in the standard way vastly overestimates the number of PBHs, by many orders of magnitude. This is because PBHs form shortly after horizon entry, meaning modes significantly larger than the PBH are unobservable and should not affect whether a PBH forms or not—this important effect is not taken into account by smoothing the distribution in the standard fashion. We discuss alternative methods and argue that the density contrast, Δ, should be used instead as super-horizon modes are damped by a factor k{sup 2}. We make a comparison between using a Press-Schechter approach and peaks theory, finding that the two are in close agreement in the region of interest. We also investigate the effect of varying the spectral index, and the running of the spectral index, on the abundance of primordial black holes.

  11. Lightning and Mass Independent Oxygen Isotopic Fractionation in Nebular Silicates

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A.

    2009-01-01

    Lightning has long been postulated as the agent of Chondru|e formation in the solar nebula, but it may have an additional role to play as well. Lightning bolts of almost any scale will both vaporize dust and liberate oxygen atoms that will then interact with both nebular gases as well as the refractory silicate vapor as it re-condenses. Such processes should result in the addition of the heavy oxygen isotopes to the growing silicate grains while the light oxygen-16 becomes part of the gas phase water. This process will proceed to some extent throughout the history of any turbulent nebula and will result in the gradual increase of O-16 in the gas phase and in a much larger relative increase in the O-17 and O-18 content of the nebular dust. Laboratory experiments have demonstrated the production of such "heavy oxygen enriched", non-mass-dependently-fractionated dust grains in a high voltage discharge in a hydrogen rich gas containing small quantities of silane, pentacarbonyl iron and oxygen.

  12. Aerosol Organic Matter-Trace Metal Relationships Revealed by Ultra-High Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Wozniak, A. S.; Sleighter, R. L.; Morton, P. L.; Landing, W. M.; Shelley, R. U.; Hatcher, P. G.

    2011-12-01

    Atmospheric delivery of aerosols is important for the biogeochemical cycling of organic matter (OM) and trace elements in marine environments. Aerosols over marine environments can be derived from marine sources or transported from continental regions of variable vegetative cover and anthropogenic influence. These different sources are key determinants of aerosol OM composition, as well as trace metal amounts and characteristics. Dust-influenced aerosols typically contain higher amounts of Fe than anthropogenic-influenced aerosols but have lesser % of soluble Fe (%FeS), believed to be the bioavailable form of Fe for marine phytoplankton. Four samples from the 2008 GEOTRACES intercalibration experiments (Miami, FL, USA) were analyzed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and related to both air mass back trajectories and %FeS. Three samples showed aerosol sources from the east consistent with Saharan dust inputs, while the fourth sample was derived in part from air masses to the north, influenced by the North American continent. This North American-influenced sample was collected following the 3 day period with the highest %FeS (1.3-1.7%) of the 11 day intercalibration experiment (mean = 0.4-1.1%). FT-ICR mass spectra showed 795 peaks common to the dust-influenced samples but absent from the North American-influenced sample. These peaks were assigned molecular formulas characterized by CHO and CHON compounds with lower H/C and O/C ratios than the 1257 formulas common to all 4 samples, suggesting that the dust-influenced aerosols carry OM that is less oxygenated and more condensed in structure along with Fe of lesser solubility. Air mass trajectory analyses revealed samples collected during a 2010 cruise in the North Atlantic Ocean to be characterized by European-influenced (anthropogenic), African-influenced (dust), and primarily marine air masses, making them ideal for further exploration of the

  13. Effects of anthropogenic emissions on the molecular composition of urban organic aerosols: An ultrahigh resolution mass spectrometry study

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; O'Connor, I. P.; Giorio, C.; Fuller, S. J.; Kristensen, K.; Maenhaut, W.; Wenger, J. C.; Sodeau, J. R.; Glasius, M.; Kalberer, M.

    2014-06-01

    Identification of the organic composition of atmospheric aerosols is necessary to develop effective air pollution mitigation strategies. However, the majority of the organic aerosol mass is poorly characterized and its detailed analysis is a major analytical challenge. In this study, we applied state-of-the-art direct infusion nano-electrospray (nanoESI) ultrahigh resolution mass spectrometry (UHRMS) and liquid chromatography ESI Quadrupole Time-of-Flight (Q-TOF) MS for the analysis of the organic fraction of fine particulate matter (PM2.5) collected at an urban location in Cork, Ireland. Comprehensive mass spectral data evaluation methods (e.g., Kendrick Mass Defect and Van Krevelen) were used to identify compound classes and mass distributions of the detected species. Up to 850 elemental formulae were identified in negative mode nanoESI-UHR-MS. Nitrogen and/or sulphur containing organic species contributed up to 40% of the total identified formulae and exhibited strong diurnal variations suggesting the importance of night-time NO3 chemistry at the site. The presence of a large number of oxidised aromatic and nitroaromatic compounds in the samples indicated a strong anthropogenic influence, i.e., from traffic emissions and domestic solid fuel (DSF) burning. Most of the identified biogenic secondary organic aerosol (SOA) compounds are later-generation nitrogen- and sulphur-containing products, indicating that SOA composition is strongly affected by anthropogenic species such as NOx and SO2. Unsaturated and saturated C12-C20 fatty acids were found to be the most abundant homologs with a composition reflecting a primary marine origin. The results of this work demonstrate that the studied site is a very complex environment affected by a variety of anthropogenic activities and natural sources.

  14. Characterization of near-highway submicron aerosols in New York City with a high-resolution time-of-flight aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Sun, Y. L.; Zhang, Q.; Schwab, J. J.; Chen, W.-N.; Bae, M.-S.; Hung, H.-M.; Lin, Y.-C.; Ng, N. L.; Jayne, J.; Massoli, P.; Williams, L. R.; Demerjian, K. L.

    2011-11-01

    Knowledge of the variations of mass concentration, chemical composition and size distributions of submicron aerosols near roadways is of importance for reducing exposure assessment uncertainties in health effects studies. The goal of this study is to deploy and evaluate an Atmospheric Sciences Research Center-Mobile Laboratory (ASRC-ML), equipped with a suite of rapid response instruments for characterization of traffic plumes, adjacent to the Long Island Expressway (LIE) - a high-traffic highway in the New York City Metropolitan Area. In total, four measurement periods, two in the morning and two in the evening were conducted at a location approximately 30 m south of the LIE. The mass concentrations and size distributions of non-refractory submicron aerosol (NR-PM1) species were measured in situ at a time resolution of 1 min by an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer, along with rapid measurements (down to 1 Hz) of gaseous pollutants (e.g., HCHO, NO2, NO, O3, and CO2, etc.), black carbon (BC), and particle number concentrations and size distributions. The particulate organics varied dramatically during periods with highest traffic influences from the nearby roadway. The variations were mainly observed in the hydrocarbon-like organic aerosol (HOA), a surrogate for primary OA from vehicle emissions. The inorganic species (sulfate, ammonium, and nitrate) and oxygenated OA (OOA) showed much smoother variations - with minor impacts from traffic emissions. The concentration and chemical composition of NR-PM1 also varied differently on different days depending on meteorology, traffic intensity and vehicle types. Overall, organics dominated the traffic-related NR-PM1 composition (>60%) with HOA being the major fraction of OA. The traffic-influenced organics showed two distinct modes in mass-weighted size distributions, peaking at ~120 nm and 500 nm (vacuum aerodynamic diameter, Dva), respectively. OOA and inorganic species appear to be

  15. 40 CFR Table 4 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in the.... Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent by mass Aliphatic b 0.03...

  16. 40 CFR Table 6 to Subpart Kkkk of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the.... Solvent/solvent blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  17. 40 CFR Table 3 to Subpart Rrrr of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the...: Solvent/Solvent blend CAS. No. Average organic HAP mass fraction Typical organic HAP, percent by mass...

  18. 40 CFR Table 4 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in the.... Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent by mass Aliphatic b 0.03...

  19. 40 CFR Table 4 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction... formulation data. Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  20. 40 CFR Table 4 to Subpart Rrrr of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups 1

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Petroleum Solvent Groups 1 You May Use the Mass Fraction Values in the...: Solvent type Average organic HAP mass fraction Typical organic percent HAP, by mass Aliphatic 2 0.03...

  1. 40 CFR Table 6 to Subpart Kkkk of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the.... Solvent/solvent blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  2. 40 CFR Table 5 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction... formulation data: Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  3. 40 CFR Table 6 to Subpart Kkkk of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the.... Solvent/solvent blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  4. 40 CFR Table 3 to Subpart Rrrr of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the...: Solvent/Solvent blend CAS. No. Average organic HAP mass fraction Typical organic HAP, percent by mass...

  5. 40 CFR Table 3 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the... Solvent/solvent blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  6. 40 CFR Table 5 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction... formulation data: Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  7. 40 CFR Table 4 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in the... Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent by mass Aliphatic b 0.03...

  8. 40 CFR Table 4 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in the... Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent by mass Aliphatic b 0.03...

  9. 40 CFR Table 3 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the... Solvent/solvent blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  10. 40 CFR Table 4 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction... formulation data. Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent by mass...

  11. 40 CFR Table 4 to Subpart Rrrr of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups 1

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for... Organic HAP Mass Fraction for Petroleum Solvent Groups 1 You May Use the Mass Fraction Values in the...: Solvent type Average organic HAP mass fraction Typical organic percent HAP, by mass Aliphatic 2 0.03...

  12. 40 CFR Table 5 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the.... Solvent/solvent blend CAS. No. Average organic HAP mass fraction Typical organic HAP, percent by mass...

  13. Molecular composition of aged secondary organic aerosol generated from a mixture of biogenic volatile compounds using ultrahigh resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Doussin, J.-F.; Giorio, C.; Mahon, B.; Wilson, E. M.; Maurin, N.; Pangui, E.; Venables, D. S.; Wenger, J. C.; Kalberer, M.

    2015-02-01

    Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidised molecules. Aerosol processing or further oxidation (ageing) of organic aerosol has been suggested to be responsible for their formation through heterogeneous uptake of oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several ageing processes on the molecular composition of secondary organic aerosols (SOA) using direct infusion and liquid chromatography ultrahigh resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC): α-pinene, β-pinene, Δ3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated ageing was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC) and elemental O/C ratios of the SOA components. None of the ageing processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using α-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH radical-initiated α-pinene oxidation had a significantly higher overall OSC and O/C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidised species in ambient biogenic SOA.

  14. Chemical composition, sources, and processes of urban aerosols during summertime in Northwest China: insights from High Resolution Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Xu, J.; Zhang, Q.; Chen, M.; Ge, X.; Ren, J.; Qin, D.

    2014-06-01

    An aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed along with a Scanning Mobility Particle Sizer (SMPS) and a Multi Angle Absorption Photometers (MAAP) to measure the temporal variations of the mass loading, chemical composition, and size distribution of sub-micrometer particulate matter (PM1) in Lanzhou, northwest China, during 12 July-7 August 2012. The average PM1 mass concentration including non-refractory PM1 (NR-PM1) measured by HR-ToF-AMS and black carbon (BC) measured by MAAP during this study was 24.5 μg m-3 (ranging from 0.86 to 105μg m-3), with a mean composition consisting of 47% organics, 16% sulfate, 12% BC, 11% ammonium, 10% nitrate, and 4% chloride. The organics was consisted of 70% carbon, 21% oxygen, 8% hydrogen, and 1% nitrogen, with the average oxygen-to-carbon ratio (O / C) of 0.33 and organic mass-to-carbon ratio (OM / OC) of 1.58. Positive matrix factorization (PMF) of the high-resolution mass spectra of organic aerosols (OA) identified four distinct factors which represent, respectively, two primary OA (POA) emission sources (traffic and food cooking) and two secondary OA (SOA) types - a fresher, semi-volatile oxygenated OA (SV-OOA) and a more aged, low-volatility oxygenated OA (LV-OOA). Traffic-related hydrocarbon-like OA (HOA) and BC displayed distinct diurnal patterns both with peak at ~07:00-11:00 (BJT: UTC +8) corresponding to the morning rush hours, while cooking OA (COA) peaked during three meal periods. The diurnal profiles of sulfate and LV-OOA displayed a broad peak between ∼07:00-15:00, while those of nitrate, ammonium, and SV-OOA showed a narrower peak at ~08:00-13:00. The later morning and early afternoon peak in the diurnal profiles of secondary aerosol species was likely caused by mixing down of pollutants aloft, which were likely produced in the residual layer decoupled from the boundary layer during night time. The mass spectrum of SV-OOA also showed similarity with that of

  15. Single particle characterization using a light scattering module coupled to a time-of-flight aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Cross, E. S.; Onasch, T. B.; Canagaratna, M.; Jayne, J. T.; Kimmel, J.; Yu, X.-Y.; Alexander, M. L.; Worsnop, D. R.; Davidovits, P.

    2008-12-01

    We present the first single particle results obtained using an Aerodyne time-of-flight aerosol mass spectrometer coupled with a light scattering module (LS-ToF-AMS). The instrument was deployed at the T1 ground site approximately 40 km northeast of the Mexico City Metropolitan Area (MCMA) as part of the MILAGRO field study in March of 2006. The instrument was operated as a standard AMS from 12-30 March, acquiring average chemical composition and size distributions for the ambient aerosol, and in single particle mode from 27-30 March. Over a 75-h sampling period, 12 853 single particle mass spectra were optically triggered, saved, and analyzed. The correlated optical and chemical detection allowed detailed examination of single particle collection and quantification within the LS-ToF-AMS. The single particle data enabled the mixing states of the ambient aerosol to be characterized within the context of the size-resolved ensemble chemical information. The particulate mixing states were examined as a function of sampling time and most of the particles were found to be internal mixtures containing many of the organic and inorganic species identified in the ensemble analysis. The single particle mass spectra were deconvolved, using techniques developed for ensemble AMS data analysis, into HOA, OOA, NH4NO3, (NH4)2SO4, and NH4Cl fractions. Average single particle mass and chemistry measurements are shown to be in agreement with ensemble MS and PTOF measurements. While a significant fraction of ambient particles were internal mixtures of varying degrees, single particle measurements of chemical composition allowed the identification of time periods during which the ambient ensemble was externally mixed. In some cases the chemical composition of the particles suggested a likely source. Throughout the full sampling period, the ambient ensemble was an external mixture of combustion-generated HOA particles from local sources (e.g. traffic), with number concentrations peaking

  16. On the Interpretation of Oxygenated Organic Aerosols (and their Subtypes) Arising from Factor Analysis of Aerosol Mass Spectrometer Data

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; Zhang, Q.; Canagaratna, M. R.; Ulbrich, I. M.; Ng, N. L.; Aiken, A. C.; Decarlo, P. F.; Kroll, J.; Mohr, C.; Allan, J. D.; Worsnop, D. R.

    2008-12-01

    Zhang et al. (ES&T 2005; ACP 2005) first performed factor analysis (FA) of Aerodyne Aerosol Mass Spectrometer (AMS) complete organic aerosol (OA) mass spectra. This study showed that an oxygenated organic aerosol (OOA) factor accounted for 2/3 of the OA mass at an urban site in Pittsburgh and strongly linked OOA to secondary organic aerosols (SOA). Many subsequent studies and the application of more powerful solution algorithms such as Positive Matrix Factorization (PMF) to the same FA problem have demonstrated the importance of OOA at most locations (e.g. Volkamer et al., GRL, 2006; Zhang et al., GRL, 2007; Lanz et al., ACP, 2007 and ES&T, 2008; Ulbrich et al., ACPD, 2008). Multiple studies have also identified several subtypes of OOA (e.g. OOA-1 and OOA-2). This type of analysis offers new insights because it provides some chemical resolution on the total OA mass with high time and size resolution, and bypasses the limitations of techniques that only analyze tracers and which may favor more reduced species. However the chemical resolution is limited and careful interpretation of the FA output is required, including the use of database spectra, time series of external tracers, tracer ratios, back-trajectory analyses, size- distribution analyses, etc. This presentation will address the interpretation of total OOA and its subfactors across a large range of locations in urban, suburban, rural, remote, and forested areas, and will compare with the results of other source apportionment techniques. Based on data from multiple datasets we conclude that (1) anthropogenic SOA in and downwind of urban areas is an important source of OOA; (2) motor vehicles, meat cooking, and trash burning are unlikely to be sources of primary OOA; (3) SOA from biogenic and biomass burning precursors are also clear sources of OOA; (4) primary biomass burning OA (P-BBOA) typically shows significant differences with ambient OOA factors; (5) heterogeneous oxidation of urban POA may give rise to

  17. FRACTIONAL AEROSOL FILTRATION EFFICIENCY OF IN-DUCT VENTILATION AIR CLEANERS

    EPA Science Inventory

    The filtration efficiency of ventilation air cleaners is highly particle-size dependent over the 0.01 to 3 μm diameter size range. Current standardized test methods, which determine only overall efficiencies for ambient aerosol or other test aerosols, provide data of limited util...

  18. Mass spectrometry of atmospheric aerosols--recent developments and applications. Part II: On-line mass spectrometry techniques.

    PubMed

    Pratt, Kerri A; Prather, Kimberly A

    2012-01-01

    Many of the significant advances in our understanding of atmospheric particles can be attributed to the application of mass spectrometry. Mass spectrometry provides high sensitivity with fast response time to probe chemically complex particles. This review focuses on recent developments and applications in the field of mass spectrometry of atmospheric aerosols. In Part II of this two-part review, we concentrate on real-time mass spectrometry techniques, which provide high time resolution for insight into brief events and diurnal changes while eliminating the potential artifacts acquired during long-term filter sampling. In particular, real-time mass spectrometry has been shown recently to provide the ability to probe the chemical composition of ambient individual particles <30 nm in diameter to further our understanding of how particles are formed through nucleation in the atmosphere. Further, transportable real-time mass spectrometry techniques are now used frequently on ground-, ship-, and aircraft-based studies around the globe to further our understanding of the spatial distribution of atmospheric aerosols. In addition, coupling aerosol mass spectrometry techniques with other measurements in series has allowed the in situ determination of chemically resolved particle effective density, refractive index, volatility, and cloud activation properties.

  19. Insights Into Water-Soluble Organic Aerosol Sources From Carbon-13 Ratios of Size Exclusion Chromatography Fractions

    NASA Astrophysics Data System (ADS)

    Ruehl, C. R.; Chuang, P. Y.; McCarthy, M. D.

    2008-12-01

    Many sources of organic aerosols have been identified and quantified, and much of this work has used individual (mosty water-insoluble) compounds as tracers of primary sources. However, most organic aerosol cannot be molecularly characterized, and the water-soluble organic carbon (WSOC) in many aerosols is thought to originate from gaseous precursors (i.e., it is secondary in nature). It can therefore be difficult to infer aerosol sources, particularly of background (i.e., aged) aerosols, and of the relatively high-MW component of aerosols. The stable isotope ratios (δ13C) of organic aerosols have been used to distinguish between sources, with lighter values (-30‰ to -25‰) interpreted as having originated from fossil fuel combustion and C4 biogenic emission, and heavier values (-25‰ to - 20‰) indicating a marine or C3 biogenic source. Most published measurements were of either total suspended particulates or PM2.5, however, and it is unknown to what extent these fractions differ from submicron WSOC. We report δ13C for submicron WSOC collected at a variety of sites, ranging from marine to polluted to background continental. Bulk marine organic δ13C ranged from -30.4 to - 27.6‰, slightly lighter than previously published results. This could be due to the elimination of supermicron cellular material or other biogenic primary emissions from the sample. Continental WSOC δ13C ranged from -19.1 to -29.8‰, with heavier values (-19.8 ± 1.0‰) in Oklahoma and lighter values at Great Smoky Mountain National Park in Tennessee (-25.8 ± 2.6‰) and Illinois (-24.5 ± 1.0‰). This likely results from the greater proportional of C3 plant material in the Oklahoma samples. In addition to bulk samples, we used size exclusion chromatography (SEC) to report δ13C of organic aerosols as a function of hydrodynamic diameter. Variability and magnitude of hydrodynamic diameter was greatest at low SEC pH, indicative of the acidic character of submicron WSOC. Tennessee

  20. Water-soluble organic carbon (WSOC) and its temperature-resolved carbon fractions in atmospheric aerosols in Beijing

    NASA Astrophysics Data System (ADS)

    Tang, Xiong; Zhang, Xiaoshan; Wang, Zhangwei; Ci, Zhijia

    2016-11-01

    Investigation of temperature-resolved carbon fractions of water-soluble organic carbon (WSOC) can improve our understanding of the chemical properties, formation processes and sources of WSOC in aerosols. We developed a method that can examine different temperature-resolved carbon fractions of WSOC and used this method to characterize aerosol samples (n = 102) collected from an urban site in Beijing in 2010-2011. The aerosol composition data including inorganic ions, elements and temperature-resolved carbon fractions of WSOC were used as input of positive matrix factorization (PMF) model to investigate the sources of WSOC. The results showed that the mean concentrations of WSOC were 10.2 μg m- 3 with increased values in winter and decreased values in summer, while WSOC/OC ratios (mean: 51.7%) were higher in spring and summer than in fall and winter. The sampling artifacts of WSOC (18.2%) were higher than those of OC (13.4%). Though WSOC was significantly influenced by biomass burning in spring and winter, the strong correlations between WSOC and other secondary components suggested that WSOC was secondary in nature. Results of temperature-resolved carbon fractions of OC and WSOC showed that WSOC/OC ratios for different carbon fractions had the highest value of 0.92 and lowest value of 0.30. PMF analysis identified four factors, three of which were associated with three organic polar compounds groups (low, medium, and high molecular weight compounds) based on their thermal evolution features, and one of which was attributed to inorganic secondary formation processes. Annually, the contributions of four factors were 20.5%, 46.2%, 12.4% and 20.9%, respectively.

  1. Mass Independent Fractionation of Hg Isotopes Preserved in the Precambrian

    NASA Astrophysics Data System (ADS)

    Thibodeau, A. M.; Bergquist, B. A.; Kah, L. C.; Ono, S.; Ghosh, S.; Hazen, R. M.

    2013-12-01

    Mercury (Hg) is a photochemically active, redox-sensitive, chalcophilic metal with complex biogeochemistry that displays a wide range of mass-dependent (MDF) and mass-independent (MIF) stable isotopic fractionation. In the past decade, Hg isotopes have emerged as important tracers of both the sources and cycling of Hg in the modern environment. However, their utility as environmental proxies in ancient rocks remains largely unexplored. The potential of Hg isotopes to inform Precambrian environments derives from the observation that Hg isotopes with odd atomic mass numbers (199Hg and 201Hg) undergo large MIF by the magnetic isotope effect (MIE) and smaller MIF through the nuclear volume effect (NVE). Small MIF produced via NVE has been observed for numerous transformations and is characterized by MIF ratios (Δ199Hg/Δ201Hg) of about 1.6. Large Hg-MIF driven by MIE has been observed during photochemical transformations and is characterized by Δ199Hg/Δ201Hg ratios between 1 and 1.3. This MIF signal is sensitive to a range of environmental conditions, including the amount and type of solar radiation, the presence and type of complexing organic ligands, and the Hg/dissolved organic carbon (DOC) ratio. Thus, it is hoped that Hg-MIF signals may indirectly record changes in atmospheric composition or seawater chemistry if preserved in marine sedimentary records. Previous work has clearly demonstrated that Hg-MIF signals are preserved in Archean and Paleoproterozoic marine shales and massive sulfide deposits. Here, we present evidence that such signals are also preserved in marine shales of mid-Proterozoic age, including the ~1.3 Ga Sulky formation (Dismal Lakes Group, NW Arctic), the ~1.45 Ga Greyson Shale (Belt Basin, Montana), and the ~1.5 Ga Katalsy formation (Kypry Group, Eastern European Platform). We observe that the Greyson shale and shales within the Sulky formation yield negative Hg-MIF with Δ199Hg/Δ201Hg ratios close to 1 and that Kaltasy group sediments

  2. 40 CFR Table 4 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in... formulation data. Solvent type Average organic HAP mass fraction Typical organic HAP, percent by...

  3. 40 CFR Table 3 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in... formulation data. Solvent/solvent blend CAS. No. Average organic HAP mass fraction Typical organic...

  4. 40 CFR Table 6 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in... formulation data. Solvent type Average organic HAP mass fraction Typical organic HAP, percent by...

  5. 40 CFR Table 4 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in... formulation data. Solvent type Average organic HAP mass fraction Typical organic HAP, percent by...

  6. 40 CFR Table 4 to Subpart Mmmm of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Part 63—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction... formulation data. Solvent type Average organic HAP mass fraction Typical organic HAP, percent by...

  7. 40 CFR Table 4 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction... formulation data. Solvent/solvent blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP,...

  8. 40 CFR Table 5 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in... formulation data. Solvent/solvent blend CAS. No. Average organic HAP mass fraction Typical organic...

  9. 40 CFR Table 4 to Subpart Mmmm of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Part 63—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction... formulation data. Solvent type Average organic HAP mass fraction Typical organic HAP, percent by...

  10. 40 CFR Table 5 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in... formulation data. Solvent/solvent blend CAS. No. Average organic HAP mass fraction Typical organic...

  11. 40 CFR Table 3 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in... formulation data. Solvent/solvent blend CAS. No. Average organic HAP mass fraction Typical organic...

  12. 40 CFR Table 4 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction... formulation data. Solvent/solvent blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP,...

  13. 40 CFR Table 4 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in... formulation data. Solvent type Average organic HAP mass fraction Typical organic HAP, percent by...

  14. 40 CFR Table 3 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in... formulation data. Solvent/solvent blend CAS. No. Average organic HAP mass fraction Typical organic...

  15. 40 CFR Table 6 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for...—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in... formulation data. Solvent type Average organic HAP mass fraction Typical organic HAP, percent by...

  16. Characterization of Organic Nitrogen in the Atmosphere Using High Resolution Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ge, X.; Sun, Y.; Chen, M.; Zhang, Q.

    2015-12-01

    Despite extensive efforts on characterizing organic nitrogen (ON) compounds in atmospheric aerosols and aqueous droplets, knowledge of ON chemistry is still limited, mainly due to its chemical complexity and lack of highly time-resolved measurements. This work is aimed at optimizing the method of using Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) to characterize ON compounds in atmospheric aerosols. Seventy-five pure nitrogen-containing organic compounds covering a variety of functional groups were analyzed with the HR-AMS. Our results show that ON compounds commonly produce NHx+, NOx+, which are usually attributed to inorganic N species such as ammonium and nitrate, and CH2N+ at m/z = 28, which is rarely quantified in ambient aerosol due to large interference from N2+ in the air signal. As a result, using the nitrogen-to-carbon (N/C) calibration factor proposed by Aiken et al. (2008) on average leads to ~ 20% underestimation of N/C in ambient organic aerosol. A new calibration factor of 0.79 is proposed for determining the average N/C in organics. The relative ionization efficiencies (RIEs) of different ON species, on average, are found to be consistent with the default RIE value (1.4) for the total organics. The AMS mass spectral features of various types of ON species (amines, amides, amino acids, etc.) are examined and used for characterizing ON composition in ambient aerosols. Our results indicate that submicron organic aerosol measured during wintertime in Fresno, CA contains significant amounts of amino-compounds whereas more diversified ON species, including N-containing aromatic heterocycle (e.g., imidazoles), are observed in fog waters collected simultaneously. Our findings have important implications for understanding atmospheric ON behaviors via the widespread HR-AMS measurements of ambient aerosols and droplets.

  17. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    NASA Astrophysics Data System (ADS)

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; McKinney, K.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Brito, J.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Alexander, M. L.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

    2015-10-01

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40 ‰) but varies substantially between locations, which is shown to reflect

  18. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    DOE PAGES

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; et al

    2015-10-23

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accountedmore » by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown

  19. Investigation of Aerosol Surface Area Estimation from Number and Mass Concentration Measurements: Particle Density Effect

    PubMed Central

    Ku, Bon Ki; Evans, Douglas E.

    2015-01-01

    For nanoparticles with nonspherical morphologies, e.g., open agglomerates or fibrous particles, it is expected that the actual density of agglomerates may be significantly different from the bulk material density. It is further expected that using the material density may upset the relationship between surface area and mass when a method for estimating aerosol surface area from number and mass concentrations (referred to as “Maynard’s estimation method”) is used. Therefore, it is necessary to quantitatively investigate how much the Maynard’s estimation method depends on particle morphology and density. In this study, aerosol surface area estimated from number and mass concentration measurements was evaluated and compared with values from two reference methods: a method proposed by Lall and Friedlander for agglomerates and a mobility based method for compact nonspherical particles using well-defined polydisperse aerosols with known particle densities. Polydisperse silver aerosol particles were generated by an aerosol generation facility. Generated aerosols had a range of morphologies, count median diameters (CMD) between 25 and 50 nm, and geometric standard deviations (GSD) between 1.5 and 1.8. The surface area estimates from number and mass concentration measurements correlated well with the two reference values when gravimetric mass was used. The aerosol surface area estimates from the Maynard’s estimation method were comparable to the reference method for all particle morphologies within the surface area ratios of 3.31 and 0.19 for assumed GSDs 1.5 and 1.8, respectively, when the bulk material density of silver was used. The difference between the Maynard’s estimation method and surface area measured by the reference method for fractal-like agglomerates decreased from 79% to 23% when the measured effective particle density was used, while the difference for nearly spherical particles decreased from 30% to 24%. The results indicate that the use of

  20. In Situ Measurements of Aerosol Mass Concentration and Spectral Absorption in Xianghe, SE of Beijing, China

    NASA Astrophysics Data System (ADS)

    Chaudhry, Z.; Martins, V.; Li, Z.

    2005-12-01

    China's rapid industrialization over the last few decades has affected air quality in many regions of China, and even the regional climate. As a part of the EAST-AIRE (East Asian Study of Tropospheric Aerosols: an International Regional Experiment) study, Nuclepore filters were collected in two size ranges (PM10 and PM2.5) at 12 hour intervals since January 2005 at Xianghe, about 70 km southeast of Beijing. Each filter was analyzed for mass concentration, aerosol scattering and absorption efficiencies. Mass concentrations during the winter months (January-March) ranged from 9 to 459 μg/m3 in the coarse mode with an average concentration of 122 μg/m3, and from 11 to 203 μg/m3 in the fine mode with an average concentration of 45 μg/m3. While some of the extreme values are likely linked to local emissions, regional air pollution episodes also played important roles. Absorption efficiency measurements at 550 nm show very high values compared to measurements performed in the United States during the CLAMS experiment. The spectral mass absorption efficiency was measured from 350 to 2500 nm and shows large differences between the absorption properties of soil dust, black carbon, and organic aerosols. The strong spectral differences observed can be related to differences in refractive indices from the several collected species and particle size effects. The absorption properties from aerosols measured in China show large absorption efficiencies, compared to aerosols measured in the US, possibly linked to different technology practices used in these countries. For organic plus black carbon aerosols, where the refractive index seems to be relatively constant, the absorption efficiency spectral dependence for fine mode aerosols falls between 1/λ and 1/λ2. The coarse mode absorption shows much less spectral dependence.

  1. Measuring the temporal evolution of aerosol composition in a remote marine environment influenced by Saharan dust outflow using a new single particle mass spectrometer.

    NASA Astrophysics Data System (ADS)

    Marsden, Nicholas; Williams, Paul; Flynn, Michael; Taylor, Jonathan; Liu, Dantong; Allan, James; Coe, Hugh

    2016-04-01

    Refractory material constitutes a significant fraction of the atmospheric aerosol burden and has a strong influence on climate through the direct radiative effect and aerosol-cloud interactions, particularly in cold and mixed phase clouds. Composition of refractory aerosols is traditionally measured using off-line analytical techniques such as filter analyses. However, when using off-line techniques the temporal evolution of the data set is lost, meaning the measurements are difficult to relate to atmospheric processes. Recently, single particle mass spectrometry (SPMS) has proven a useful tool for the on-line study of refractory aerosols with the ability to probe size resolved chemical composition with high temporal resolution on a particle by particle basis. A new Laser Ablation Aerosol Time-of-Flight (LAAP-TOF) SPMS instrument with a modified optical detection system was deployed for ground based measurements at Praia, Cape Verde during the Ice in Cloud - Dust (ICE-D) multi-platform campaign in August 2015. A primary aim of the project was to evaluate the impact of Saharan dust on ice nucleation in mixed phase clouds. The instrument was operated over a 16 day period in which several hundred thousand single particle mass spectra were obtained from air masses with back trajectories traversing the Mid-Atlantic, Sahara Desert and West Africa. The data presented indicate external mixtures of sea salt and silicate mineral dust internally mixed with secondary species that are consistent with long range transport to a remote marine environment. The composition and size distributions measured with the LAAP-TOF are compared with measurements from an aerodynamic particle sizer (APS), Single Particle Soot Photometer (SP2), and data from SEM-EDX analysis of filter samples. The particle number fraction identified as silicate mineral from the mass spectra correlates with a fraction of the incandescent particles measured with the SP2. We discuss the suitability of the modified

  2. Aerosol mass spectrometry: particle-vaporizer interactions and their consequences for the measurements

    NASA Astrophysics Data System (ADS)

    Drewnick, F.; Diesch, J.-M.; Faber, P.; Borrmann, S.

    2015-09-01

    The Aerodyne aerosol mass spectrometer (AMS) is a frequently used instrument for on-line measurement of the ambient sub-micron aerosol composition. With the help of calibrations and a number of assumptions on the flash vaporization and electron impact ionization processes, this instrument provides robust quantitative information on various non-refractory ambient aerosol components. However, when measuring close to certain anthropogenic or marine sources of semi-refractory aerosols, several of these assumptions may not be met and measurement results might easily be incorrectly interpreted if not carefully analyzed for unique ions, isotope patterns, and potential slow vaporization associated with semi-refractory species. Here we discuss various aspects of the interaction of aerosol particles with the AMS tungsten vaporizer and the consequences for the measurement results: semi-refractory components - i.e., components that vaporize but do not flash-vaporize at the vaporizer and ionizer temperatures, like metal halides (e.g., chlorides, bromides or iodides of Al, Ba, Cd, Cu, Fe, Hg, K, Na, Pb, Sr, Zn) - can be measured semi-quantitatively despite their relatively slow vaporization from the vaporizer. Even though non-refractory components (e.g., NH4NO3 or (NH4)2SO4) vaporize quickly, under certain conditions their differences in vaporization kinetics can result in undesired biases in ion collection efficiency in thresholded measurements. Chemical reactions with oxygen from the aerosol flow can have an influence on the mass spectra for certain components (e.g., organic species). Finally, chemical reactions of the aerosol with the vaporizer surface can result in additional signals in the mass spectra (e.g., WO2Cl2-related signals from particulate Cl) and in conditioning or contamination of the vaporizer, with potential memory effects influencing the mass spectra of subsequent measurements. Laboratory experiments that investigate these particle-vaporizer interactions are

  3. Mass spectrometric airborne measurements of submicron aerosol and cloud residual composition in tropic deep convection during ACRIDICON-CHUVA

    NASA Astrophysics Data System (ADS)

    Schulz, Christiane; Schneider, Johannes; Mertes, Stephan; Kästner, Udo; Weinzierl, Bernadett; Sauer, Daniel; Fütterer, Daniel; Walser, Adrian; Borrmann, Stephan

    2015-04-01

    Airborne measurements of submicron aerosol and cloud particles were conducted in the region of Manaus (Amazonas, Brazil) during the ACRIDICON-CHUVA campaign in September 2014. ACRIDICON-CHUVA aimed at the investigation of convective cloud systems in order to get a better understanding and quantification of aerosol-cloud-interactions and radiative effects of convective clouds. For that, data from airborne measurements within convective cloud systems are combined with satellite and ground-based data. We used a C-ToF-AMS (Compact-Time-of-Flight-Aerosol-Mass-Spectrometer) to obtain information on aerosol composition and vertical profiles of different aerosol species, like organics, sulphate, nitrate, ammonium and chloride. The instrument was operated behind two different inlets: The HASI (HALO Aerosol Submicrometer Inlet) samples aerosol particles, whereas the CVI (Counterflow Virtual Impactor) samples cloud droplets and ice particles during in-cloud measurements, such that cloud residual particles can be analyzed. Differences in aerosol composition inside and outside of clouds and cloud properties over forested or deforested region were investigated. Additionally, the in- and outflow of convective clouds was sampled on dedicated cloud missions in order to study the evolution of the clouds and the processing of aerosol particles. First results show high organic aerosol mass concentrations (typically 15 μg/m3 and during one flight up to 25 μg/m3). Although high amounts of organic aerosol in tropic air over rainforest regions were expected, such high mass concentrations were not anticipated. Next to that, high sulphate aerosol mass concentrations (about 4 μg/m3) were measured at low altitudes (up to 5 km). During some flights organic and nitrate aerosol was observed with higher mass concentrations at high altitudes (10-12 km) than at lower altitudes, indicating redistribution of boundary layer particles by convection. The cloud residuals measured during in

  4. Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: linking laboratory and field studies

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Fuller, Stephen; Aalto, Juho; Healy, Robert; Alfara, Rami; Ruuskanen, Taina; Wenger, John; McFiggans, Gordon; Kulmala, Markku; Kalberer, Markus

    2013-04-01

    Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry and give rise to secondary organic aerosols (SOA), which have effects on climate and human health. Laboratory chamber experiments have been performed during several decades in an attempt to mimic atmospheric SOA formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. To date, most laboratory experiments have been performed using a single organic precursor (e.g., alpha- or beta-pinene, isoprene) while in the atmosphere a wide range of precursors contribute to SOA, which results most likely in a more complex SOA composition compared to the one-precursor laboratory systems. The objective of this work is to compare laboratory generated SOA from oxidation of BVOCs mixtures and remote ambient samples using ultrahigh-resolution mass spectrometry (UHR-MS) that allows detection of hundreds of individual SOA constituents. We examined aerosol samples from a boreal forest site, Hyytiälä, Finland and determined that a dominant fraction of the detected compounds are reaction products of a multi-component mixture of BVOCs. In the subsequent smog chamber experiments, SOA was generated from the ozonolysis and OH initiated reactions with BVOC mixtures containing species (alpha- and beta-pinene, delta-3-carene, and isoprene) that are most abundant in Hyytiälä's environment. The laboratory experiments were performed at conditions (e.g., RH, aerosol seed, and VOC ratios) that would resemble those at the boreal sampling site during the summer period. The elemental composition of the complex mixtures from laboratory generated SOA samples were compared with field samples using statistical data analysis methods.

  5. The regulation of the cold neutral gas mass fraction by turbulent motions

    NASA Astrophysics Data System (ADS)

    Gazol, A.; Villagran, M. A.

    2016-10-01

    We present results from hydrodynamic simulations with forced turbulence at a scale of 50 pc and cooling functions adapted to describe the thermal conditions at four different Galactocentric distances: 8.5, 11, 15, and 18 kpc. These experiments are aimed to study the effects of varying the turbulent velocity vrms on the cold gas mass fraction. With realistic vrms we obtain average one-dimensional cold gas mass fractions which are comparable with the observed values. Our simulations can also lead to an approximately constant cold gas mass fraction for distances ≥11 kpc when considering subsonic perturbations for 15 and 18 kpc. We also find that the average one dimensional cold gas mass fraction and the volumetric cold gas mass fraction do not follow the same radial trends.

  6. Cryptococcus neoformans glucuronoxylomannan fractions of different molecular masses are functionally distinct

    PubMed Central

    Albuquerque, Priscila C; Fonseca, Fernanda L; Dutra, Fabianno F; Bozza, Marcelo T; Frases, Susana; Casadevall, Arturo; Rodrigues, Marcio L

    2015-01-01

    Aims Glucuronoxylomannan (GXM) is the major polysaccharide component of Cryptococcus neoformans. We evaluated in this study whether GXM fractions of different molecular masses were functionally distinct. Materials & methods GXM samples isolated from C. neoformans cultures were fractionated to generate polysaccharide preparations differing in molecular mass. These fractions were used in experiments focused on the association of GXM with cell wall components of C. neoformans, as well as on the interaction of the polysaccharide with host cells. Results & conclusion GXM fractions of variable molecular masses bound to the surface of a C. neoformans acapsular mutant in a punctate pattern that is in contrast to the usual annular pattern of surface coating observed when GXM samples containing the full molecular mass range were used. The polysaccharide samples were also significantly different in their ability to stimulate cytokine production by host cells. Our findings indicate that GXM fractions are functionally distinct depending on their mass. PMID:24571070

  7. Aerosol optical depth and fine-mode fraction retrieval over East Asia using multi-angular total and polarized remote sensing

    NASA Astrophysics Data System (ADS)

    Cheng, T.; Gu, X.; Xie, D.; Li, Z.; Yu, T.; Chen, H.

    2012-03-01

    A new aerosol retrieval algorithm using multi-angular total and polarized measurements is presented. The algorithm retrieves aerosol optical depth (AOD), fine-mode fraction (FMF) for studying the impact of aerosol on climate change. The retrieval algorithm is based on a lookup table (LUT) method, which assumes that one fine and one coarse lognormal aerosol modes can be combined with proper weightings to represent the ambient aerosol properties. To reduce the ambiguity in retrieval algorithm, the key characteristics of aerosol model over East Asia are constrained using the cluster analysis technique based on the AERONET sun-photometer observation over East Asia, and the fine and coarse modes are not fixed but can vary. A mixing model of bare soil and green vegetation spectra and the Nadal and Breon model for the bidirectional polarized reflectance factor (BPDF) were used to simulate total and polarized surface reflectance of East Asia. By applying the present algorithm to POLDER measurements, three different aerosol cases of clear, polluted and dust are analyzed to test the algorithm. The comparison of retrieved aerosol optical depth (AOD) and fine-mode fraction (FMF) with those of AERONET sun-photometer observations show reliable results. Preliminary validation is encouraging. Using the new aerosol retrieval algorithm for multi-angular total and polarized measurements, the spatial and temporal variability of anthropogenic aerosol optical properties over East Asia, which were observed during a heavy polluted event, were analyzed. Exceptionally high values of aerosol optical depth contributed by fine mode of up to 0.5 (at 0.865 μm), and high values of fine-mode fraction of up to 0.9, were observed in this case study.

  8. Development and characterization of an aircraft aerosol time-of-flight mass spectrometer.

    PubMed

    Pratt, Kerri A; Mayer, Joseph E; Holecek, John C; Moffet, Ryan C; Sanchez, Rene O; Rebotier, Thomas P; Furutani, Hiroshi; Gonin, Marc; Fuhrer, Katrin; Su, Yongxuan; Guazzotti, Sergio; Prather, Kimberly A

    2009-03-01

    Vertical and horizontal profiles of atmospheric aerosols are necessary for understanding the impact of air pollution on regional and global climate. To gain further insight into the size-resolved chemistry of individual atmospheric particles, a smaller aerosol time-of-flight mass spectrometer (ATOFMS) with increased data acquisition capabilities was developed for aircraft-based studies. Compared to previous ATOFMS systems, the new instrument has a faster data acquisition rate with improved ion transmission and mass resolution, as well as reduced physical size and power consumption, all required advances for use in aircraft studies. In addition, real-time source apportionment software allows the immediate identification and classification of individual particles to guide sampling decisions while in the field. The aircraft (A)-ATOFMS was field-tested on the ground during the Study of Organic Aerosols in Riverside, CA (SOAR) and aboard an aircraft during the Ice in Clouds Experiment-Layer Clouds (ICE-L). Initial results from ICE-L represent the first reported aircraft-based single-particle dual-polarity mass spectrometry measurements and provide an increased understanding of particle mixing state as a function of altitude. Improved ion transmission allows for the first single-particle detection of species out to approximately m/z 2000, an important mass range for the detection of biological aerosols and oligomeric species. In addition, high time resolution measurements of single-particle mixing state are demonstrated and shown to be important for airborne studies where particle concentrations and chemistry vary rapidly.

  9. HUMIDITY EFFECTS ON THE MASS SPECTRA OF SINGLE AEROSOL PARTICLES. (R823980)

    EPA Science Inventory

    On-line laser desorption ionization mass spectrometry has developed into a widely used method for chemical characterization of individual aerosol particles. In the present study, the spectra of laboratory-generated particles were obtained as a function of relative humidity to elu...

  10. Determination of minimum mass and spatial location of initiator for detonation of propylene oxide aerosols

    NASA Astrophysics Data System (ADS)

    Apparao, A.; Saji, J.; Balaji, M.; Devangan, A. K.; Rao, C. R.

    2016-06-01

    The mishandling of liquid fuels during production, processing or transportation can lead to the formation of combustible two-phase mixtures. These mixtures, with the availability of a suitable energy source, may be ignited generating a deflagration, or even a detonation wave. For military applications, unconfined fuel aerosols are created and detonated with the help of a strong shock generated by a powerful energy source. The minimum energy requirement is expressed in terms of the shock strength, or mass of the high-explosive-based initiator. In this study, the detonability of unconfined aerosols of 4.3 kg propylene oxide was studied by positioning different quantities of cylindrical-shaped initiators of RDX/wax (95/5) at a fixed spatial location in the aerosol cloud, and the minimum mass of the initiator required for detonation initiation was determined. The effect of spatial location and the requirement of initiator mass, especially at farther locations where the fuel concentration is likely to be lower and closer to the lower explosive limit, was also investigated. The experimental findings help identify the detonable zone in unconfined propylene oxide aerosol clouds for different combinations of spatial location and mass of initiator.

  11. Chemical characterization of the ambient organic aerosol soluble in water: 1. Isolation of hydrophobic and hydrophilic fractions with a XAD-8 resin

    NASA Astrophysics Data System (ADS)

    Sullivan, Amy P.; Weber, Rodney J.

    2006-03-01

    Group separation of the aqueous extract of fine particles bearing water-soluble organic carbon (WSOC) provides unique insights into the sources of organic carbon (OC). XAD-8 resin coupled with a Total Organic Carbon analyzer allows for direct quantification. We term the fraction of WSOC not retained by a XAD-8 resin column at pH 2 as hydrophilic WSOC (WSOCxp); this includes saccharides, amines, and carbonyls and aliphatic monocarboxylic/dicarboxylic/oxocarboxylic acids with less than 4 or 5 carbons. The fraction of WSOC retained by XAD-8, termed the hydrophobic fraction (WSOCxr), include aromatic acids, phenols, organic nitrates, cyclic acids, and carbonyls and monocarboxylic/dicarboxylic acids with greater than 3 or 4 carbons. However, only aromatic compounds (or aromatic-like compounds with similar properties) can subsequently be extracted from XAD-8 with high efficiency. By coupling a Particle-into-Liquid Sampler with this technique, online measurements of WSOC, WSOCxp, and WSOCxr are possible. Urban measurements from St. Louis and Atlanta, on a carbon mass basis, show an increase in the mean WSOC fraction from winter (51%) to summer (61%), due to increases in the WSOCxp/OC from 0.25 to 0.35. During a summer Atlanta PM event, WSOC to OC was 0.75, driven largely by increases in the WSOCxp. The results are consistent with the view that in the summer, there are increased amounts of oxygenated polar compounds, possibly from secondary organic aerosol production, and that these compounds account for an even larger fraction of OC during stagnation events. A companion paper describes a method to further group speciate these XAD-8 isolated fractions.

  12. Mass concentration and mineralogical characteristics of aerosol particles collected at Dunhuang during ACE-Asia

    NASA Astrophysics Data System (ADS)

    Shen, Z. X.; Cao, J. J.; Li, X. X.; Okuda, T.; Wang, Y. Q.; Zhang, X. Y.

    2006-03-01

    Measurements were performed in spring 2001 and 2002 to determine the characteristics of soil dust in the Chinese desert region of Dunhuang, one of the ground sites of the Asia-Pacific Regional Aerosol Characterization Experiment (ACE-Asia). The mean mass concentrations of total suspended particle matter during the spring of 2001 and 2002 were 317 mu g m(-3) and 307 mu g m(-3) respectively. Eleven dust storm events were observed with a mean aerosol concentration of 1095 mu g m(-3), while the non-dusty days with calm or weak wind speed had a background aerosol loading of 196 mu g m(-3) on average in the springtime. The main minerals detected in the aerosol samples by X-ray diffraction were illite, kaolinite, chlorite, quartz, feldspar, calcite and dolomite. Gypsum, halite and amphibole were also detected in a few samples. The mineralogical data also show that Asian dust is characterized by a kaolinite to chlorite (K/C) ratio lower than 1 whereas Saharan dust exhibits a K/C ratio larger than 2. Air mass back- trajectory analysis show that three families of pathways are associated with the aerosol particle transport to Dunhuang, but these have similar K/C ratios, which further demonstrates that the mineralogical characteristics of Asian dust are different from African dust.

  13. In situ submicron organic aerosol characterization at a boreal forest research station during HUMPPA-COPEC 2010 using soft and hard ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Corrigan, A. L.; Junninen, H.; Ehn, M.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Russell, L. M.; Williams, J.; Hoffmann, T.

    2013-11-01

    , contained organic compounds up to 800 Da (MWom≈450 g mol-1), showing that the average molecular weight can vary significantly. The high measurement frequency of both AMS and APCI-IT-MS enabled the partitioning of selected organic acids between gas and particle phase as a function of the total particulate mass to be quantified. Surprisingly high fractions of the higher molecular weight organic acids were observed to reside in the gas phase. These observations might be a consequence of large equilibration timescales for semi-solid boreal forest aerosol, as has been recently hypothesized by Shiraiwa and Seinfeld (2012).

  14. In-situ submicron organic aerosol characterization at a boreal forest research station during HUMPPA-COPEC 2010 using soft and hard ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Corrigan, A. L.; Junninen, H.; Ehn, M.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Russell, L. M.; Williams, J.; Hoffmann, T.

    2013-07-01

    , contained organic compounds up to 800 Da (MWom ≈ 450 g mol-1), showing that the average molecular weight can vary significantly. The high measurement frequency of both, AMS and APCI-IT-MS, enabled the partitioning of selected organic acids between gas- and particle-phase as a function of the total particulate mass to be quantified. Surprisingly high fractions of the higher molecular weight organic acids were observed to reside in the gas phase. These observations might be a consequence of large equilibration timescales for semi-solid boreal forest aerosol, as it has been recently hypothesised by Shiraiwa and Seinfeld (2012).

  15. Size-Segregated Aerosol Composition and Mass Loading of Atmospheric Particles as Part of the Pacific Northwest 2001(PNW2001) Air Quality Study In Puget Sound

    NASA Astrophysics Data System (ADS)

    Disselkamp, R. S.; Barrie, L. A.; Shutthanadan, S.; Cliff, S.; Cahill, T.

    2001-12-01

    In mid-August, 2001, an aircraft-based air-quality study was performed in the Puget Sound, WA, area entitled PNW2001 (http://www.pnl.gov/pnw2001). The objectives of this field campaign were the following: 1. reveal information about the 3-dimensional distribution of ozone, its gaseous precursors and fine particulate matter during weather conditions favoring air pollution; 2. derive information about the accuracy of urban and biogenic emissions inventories that are used to drive the air quality forecast models; and 3. examine the accuracy of modeled ozone concentration with that observed. In support of these efforts, we collected time-averaged ( { ~}10 minute averages), size-segregated, aerosol composition and mass-loading information using ex post facto analysis techniques of synchrotron x-ray fluorescence (s-XRF), proton induced x-ray emissions(PIXE), proton elastic scattering (PESA), and scanning transmission ion microscopy (STIM). This is the first time these analysis techniques have been used together on samples collected from aircraft using an optimized 3-stage rotating drum impactor. In our presentation, we will discuss the aerosol components in three aerosol size fractions as identified by statistical analysis of multielemental data (including total mass, H, Na, Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Pb) and relate variations in these components to physical aerosol properties, other gaseous trace constituents and to air mass origin.

  16. Aerosol Charge Model Consistent with Flight Data from the ECOMA/MASS Rocket Campaign

    NASA Astrophysics Data System (ADS)

    Knappmiller, S.; Robertson, S. H.; Rapp, M.; Gumbel, J.; Horanyi, M.; Sternovsky, Z.; Friedrich, M.; Baumgarten, G.; Latteck, R.

    2009-12-01

    In August of 2007 two sounding rockets were launched from the Andoya Rocket Range, Norway carrying the MASS instrument (Mesospheric Aerosol Sampling Spectrometer). The instrument detects charged aerosols in four different mass ranges on four pairs of biased collector plates, one set for positive particles and one set for negative particles. The first sounding rocket was launched into PMSE and NLC on 3 August. The solar zenith angle was 93 degrees and NLC were seen in the previous hour at 83 km by the ALOMAR RMR lidar. NLC were also detected at the same altitude by rocket-borne photometer measurements. The data from the MASS instrument shows a negatively charged population with radii >3 nm in the 83-89 km altitude range, which is collocated with PMSE detected by the ALWIN radar. Smaller particles, 1-2 nm in radius with both positive and negative polarity were detected between 86-88 km. Positively charged particles <1 nm in radius were detected at the same altitude. A charging model is developed to investigate the coexistence of positively and negatively charged aerosols in the NLC environment. Natanson’s rate equations are used for the attachment of free electrons and ions and the model includes charging by photo-electron emission and photo-detachment. Although the MASS flight occurred during night time conditions, the solar flux was still significant to affect the charge state of the aerosols. The calculations are done assuming three types of particles with different photo-electron charging properties: 1) Icy NLC particles, 2) Hematite particles of meteoric origin as condensation nuclei, and 3) Hematite particles coated with ice. The charge model results are consistent with the MASS rocket data, displaying both positively and negatively charged aerosols for small radii and only negatively charged particles for large radii.

  17. In-Flight Chemical Composition Observations of Aircraft Emissions using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Ziemba, L. D.; Martin, R.; Moore, R.; Shook, M.; Thornhill, K. L., II; Winstead, E.; Anderson, B. E.

    2015-12-01

    Commercial aircraft are an important source of aerosols to the upper troposphere. The microphysical and chemical properties of these emitted aerosols govern their ability to act as ice nuclei, both in near-field contrails and for cirrus formation downstream. During the ACCESS-II (Alternative Fuel Effects on Contrails and Cruise Emissions) campaign, NASA DC-8 CFM56-2-C1 engine emissions were sampled systematically at a range of cruise-relevant thrust levels and at several altitudes. Sampling was done aboard the NASA HU-25 Falcon aircraft, which was equipped with a suite of aerosol and gas-phase instruments focused on assessing the effects of burning different fuel mixtures on aerosol properties and their associated contrails. Here we present in-flight measurements of particle chemical composition made by a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). The AMS was able to sufficiently resolve near-field (within 100m) aircraft emissions plumes. Low-sulfur HEFA (hydro-processed esters and fatty-acids) and JetA fuels yielded particles that contained 11 and 8% sulfate, respectively, compared to 30% sulfate contribution for traditional JetA fuel. Each of the fuels produced organic aerosol with similarly low oxygen content. Lubrication oils, which are not a combustion product but result from leaks in the engine, were likely a dominant fraction of the measured organic mass based on mass-spectral marker analysis. These results are compared to similar engine conditions from ground-based testing.

  18. Identification of haze-creating sources from fine particulate matter in Dhaka aerosol using carbon fractions.

    PubMed

    Begum, Bilkis A; Hopke, Philip K

    2013-09-01

    Fine particulate matter (PM2.5) samples were simultaneously collected on Teflon and quartz filters between February 2010 and February 2011 at an urban monitoring site (CAMS2) in Dhaka, Bangladesh. The samples were collected using AirMetrics MiniVol samplers. The samples on Teflon filters were analyzed for their elemental composition by PIXE and PESA. Particulate carbon on quartz filters was analyzed using the IMPROVE thermal optical reflectance (TOR) method that divides carbon into four organic carbons (OC), pyrolized organic carbon (OP), and three elemental carbon (EC) fractions. The data were analyzed by positive matrix factorization using the PMF2 program. Initially, only total OC and total EC were included in the analysis and five sources, including road dust, sea salt and Zn, soil dust, motor vehicles, and brick kilns, were obtained. In the second analysis, the eight carbon fractions (OC1, OC2, OC3, OC4, OP, EC1, EC2, EC3) were included in order to ascertain whether additional source information could be extracted from the data. In this case, it is possible to identify more sources than with only total OC and EC. The motor vehicle source was separated into gasoline and diesel emissions and a fugitive Pb source was identified. Brick kilns contribute 7.9 microg/m3 and 6.0 microg/m3 of OC and EC, respectively, to the fine particulate matter based on the two results. From the estimated mass extinction coefficients and the apportioned source contributions, soil dust, brick kiln, diesel, gasoline, and the Pb sources were found to contribute most strongly to visibility degradation, particularly in the winter. PMID:24151680

  19. Characterization of particulate matter emissions from on-road gasoline and diesel vehicles using a soot particle aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Dallmann, T. R.; Onasch, T. B.; Kirchstetter, T. W.; Worton, D. R.; Fortner, E. C.; Herndon, S. C.; Wood, E. C.; Franklin, J. P.; Worsnop, D. R.; Goldstein, A. H.; Harley, R. A.

    2014-02-01

    Particulate matter (PM) emissions were measured in July 2010 from on-road motor vehicles driving through a highway tunnel in the San Francisco Bay area. A soot particle aerosol mass spectrometer (SP-AMS) was used to measure the chemical composition of PM emitted by gasoline and diesel vehicles at high time resolution. Organic aerosol (OA) and black carbon (BC) concentrations were measured during various time periods that had different levels of diesel influence, as well as directly in the exhaust plumes of individual heavy-duty (HD) diesel trucks. BC emission factor distributions for HD trucks were more skewed than OA distributions, with the highest 10% of trucks accounting for 56 and 42% of total measured BC and OA emissions, respectively. A comparison of measured OA and BC mass spectra across various sampling periods revealed a high degree of similarity in BC and OA emitted by gasoline and diesel engines. Cycloalkanes predominate in exhaust OA emissions relative to saturated alkanes (i.e., normal and iso-paraffins), suggesting that lubricating oil rather than fuel is the dominant source of primary organic aerosol (POA) emissions in diesel vehicle exhaust. This finding is supported by the detection of trace elements such as zinc and phosphorus in the exhaust plumes of individual trucks. Trace elements were emitted relative to total OA at levels that are consistent with typical weight fractions of commonly used additives present in lubricating oil. The presence of trace elements in vehicle exhaust raises the concern that ash deposits may accumulate over time in diesel particle filter systems, and may eventually lead to performance problems that require servicing.

  20. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    SciTech Connect

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-13

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  1. Correlations in the chemical composition of rural background atmospheric aerosol in the UK determined in real time using time-of-flight mass spectrometry.

    PubMed

    Beddows, David C S; Donovan, Robert J; Harrison, Roy M; Heal, Mathew R; Kinnersley, Robert P; King, Martin D; Nicholson, David H; Thompson, Katherine C

    2004-02-01

    An aerosol time-of-flight mass spectrometer (ATOFMS) was used to determine, in real time, the size and chemical composition of individual particles in the atmosphere at the remote inland site of Eskdalemuir, Scotland. A total of 51,980 particles, in the size range 0.3-7.4 microm, were detected between the 25th and 30th June 2001. Rapid changes in the number density, size and chemical composition of the atmospheric aerosol were observed. These changes are attributed to two distinct types of air mass; a polluted air mass that had passed over the British mainland before reaching Eskdalemuir, interposed between two cleaner air masses that had arrived directly from the sea. Such changes in the background aerosol could clearly be very important to studies of urban aerosols and attempts at source apportionment. The results of an objective method of data analysis are presented. Correlations were sought between the occurrence of: lithium, potassium, rubidium, caesium, beryllium, strontium, barium, ammonium, amines, nitrate, nitrite, boron, mercury, sulfate, phosphate, fluorine, chlorine, bromine, iodine and carbon (both elemental and organic hydrocarbon) in both fine (d < 2.5 microm) and coarse (d > 2.5 microm) particle fractions. Several previously unreported correlations were observed, for instance between the elements lithium, beryllium and boron. The results suggest that about 2 in 3 of all fine particles (by number rather than by mass), and 1 in 2 of all coarse particles containing carbon, consisted of elemental carbon rather than organic hydrocarbon (although a bias in the sensitivity of the ATOFMS could have affected these numbers). The ratio of the number of coarse particles containing nitrate anions to the number of particles containing chloride anions exceeded unity when the air mass had travelled over the British mainland. The analysis also illustrates that an air mass of marine origin that had travelled slowly over agricultural land can accumulate amines and

  2. Organic Mass to Organic Carbon ratio in Atmospheric Aerosols: Observations and Global Simulations

    NASA Astrophysics Data System (ADS)

    Tsigaridis, K.; Kanakidou, M.; Daskalakis, N.

    2012-12-01

    Organic compounds play an important role in atmospheric chemistry and affect Earth's climate through their impact on oxidants and aerosol formation (e.g. O3 and organic aerosols (OA)). Due to the complexity of the mixture of organics in the atmosphere, the organic-mass-to-organic-carbon ratio (OM/OC) is often used to characterize the organic component in atmospheric aerosols. This ratio varies dependant on the aerosol origin and the chemical processing in the atmosphere. Atmospheric observations have shown that as OA and its precursor gases age in the atmosphere, it leads to the formation of more oxidized (O:C atomic ratio 0.6 to 0.8), less volatile and less hydrophobic compounds (particle growth factor at 95% relative humidity of 0.16 to 0.20) that have more similar properties than fresh aerosols. While reported OM:OC ratios observed over USA range between 1.29 and 1.95, indicating significant contribution of local pollution sources to the OC in that region, high O/C ratio associated with a high OM/OC ratio of 2.2 has been also observed for the summertime East Mediterranean aged aerosol. In global models, the OM/OC ratio is either calculated for specific compounds or estimated for compound groups. In the present study, we review OM/OC observations and compare them with simulations from a variety of models that contributed to the AEROCOM exercise. We evaluate the chemical processing level of atmospheric aerosols simulated by the models. A total of 32 global chemistry transport models are considered in this study with variable complexity of the representation of OM/OC ratio in the OA. The analysis provides an integrated view of the OM/OC ratio in the global atmosphere and of the accuracy of its representation in the global models. Implications for atmospheric chemistry and climate simulations are discussed.

  3. SAGE and SAM II measurements of global stratospheric aerosol optical depth and mass loading

    NASA Technical Reports Server (NTRS)

    Kent, G. S.; Mccormick, M. P.

    1984-01-01

    Several volcanic eruptions between November 1979 and April 1981 have injected material into the stratosphere. The SAGE and SAM II satellite systems have measured, with global coverage, the 1-micron extinction produced by this material, and examples of the data product are shown in the form of global maps of stratospheric optical depth and altitude-latitude plots of zonal mean extinction. These data, and that for the volcanically quiet period in early 1979, have been used to determine the changes in the total stratospheric mass loading. Estimates have also been made of the contribution to the total aerosol mass from each eruption. It has been found that between 1979 and mid-1981, the total stratospheric aerosol mass increased from a background level of approximately 570,000 metric tons to a peak of approximately 1,300,000 metric tons.

  4. 40 CFR Table 3 to Subpart Mmmm of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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    Code of Federal Regulations, 2012 CFR

    2012-07-01

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  6. 40 CFR Table 3 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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    Code of Federal Regulations, 2011 CFR

    2011-07-01

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  8. 40 CFR Table 4 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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  9. 40 CFR Table 5 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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  10. 40 CFR Table 3 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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  11. 40 CFR Table 4 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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  12. 40 CFR Table 4 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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    Code of Federal Regulations, 2012 CFR

    2012-07-01

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  14. 40 CFR Table 5 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Default Organic HAP Mass Fraction for... OOOO of Part 63—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass... manufacturer's formulation data: Solvent type Averageorganic HAP mass fraction Typical organic HAP, percent...

  15. 40 CFR Table 4 to Subpart Mmmm of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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    Code of Federal Regulations, 2014 CFR

    2014-07-01

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    Code of Federal Regulations, 2013 CFR

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  18. 40 CFR Table 3 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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  19. 40 CFR Table 3 to Subpart Mmmm of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for... MMMM of Part 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass... organic HAP mass fraction must be used for that solvent blend. Otherwise, use the organic HAP...

  20. 40 CFR Table 3 to Subpart IIIi of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Default Organic HAP Mass Fraction for... of Part 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass... manufacturer's formulation data Solvent/solvent blend CAS. No. Averageorganic HAP mass fraction Typical...

  1. Composition and effects of inhalable size fractions of atmospheric aerosols in the polluted atmosphere: part I. PAHs, PCBs and OCPs and the matrix chemical composition.

    PubMed

    Landlová, Linda; Cupr, Pavel; Franců, Juraj; Klánová, Jana; Lammel, Gerhard

    2014-05-01

    Atmospheric particulate matter (PM) abundance, mass size distribution (MSD) and chemical composition are parameters relevant for human health effects. The MSD and phase state of semivolatile organic pollutants were determined at various polluted sites in addition to the PM composition and MSD. The distribution pattern of pollutants varied from side to side in correspondence to main particle sources and PM composition. Levels of particle-associated polycyclic aromatic hydrocarbons (PAHs) were 1-30 ng m(-3) (corresponding to 15-35 % of the total, i.e., gas and particulate phase concentrations), of polychlorinated biphenyls (PCBs) were 2-11 pg m(-3) (4-26 % of the total) and of DDT compounds were 2-12 pg m(-3) (4-23 % of the total). The PM associated amounts of other organochlorine pesticides were too low for quantification. The organics were preferentially found associated with particles <0.45 μm of aerodynamic equivalent diameter. The mass fractions associated with sub-micrometer particles (PM0.95) were 73-90 %, 34-71 % and 36-81 % for PAHs, PCBs and DDT compounds, respectively. The finest particles fraction had the highest aerosol surface concentration (6.3-29.7)×10(-6) cm(-1) (44-70 % of the surface concentration of all size fractions). The data set was used to test gas-particle partitioning models for semivolatile organics for the first time in terms of the organics' MSD and size-dependent PM composition. The results of this study prove that at the various sites particles with diverse size, matrix composition, amount of contaminants and toxicological effects occur. Legislative regulation based on gravimetric determination of PM mass can clearly be insufficient for assessment.

  2. Mixing state of particles with secondary species by single particle aerosol mass spectrometer in an atmospheric pollution event

    NASA Astrophysics Data System (ADS)

    Xu, Lingling; Chen, Jinsheng

    2016-04-01

    Single particle aerosol mass spectrometer (SPAMS) was used to characterize size distribution, chemical composition, and mixing state of particles in an atmospheric pollution event during 20 Oct. - 5 Nov., 2015 in Xiamen, Southeast China. A total of 533,012 particle mass spectra were obtained and clustered into six groups, comprising of industry metal (4.5%), dust particles (2.6%), carbonaceous species (70.7%), K-Rich particles (20.7%), seasalt (0.6%) and other particles (0.9%). Carbonaceous species were further divided into EC (70.6%), OC (28.5%), and mixed ECOC (0.9%). There were 61.7%, 58.3%, 4.0%, and 14.6% of particles internally mixed with sulfate, nitrate, ammonium and C2H3O, respectively, indicating that these particles had undergone significant aging processing. Sulfate was preferentially mixed with carbonaceous particles, while nitrate tended to mix with metal-containing and dust particles. Compared to clear days, the fractions of EC-, metal- and dust particles remarkably increased, while the fraction of OC-containing particles decreased in pollution days. The mixing state of particles, excepted for OC-containing particles with secondary species was much stronger in pollution days than that in clear days, which revealed the significant influence of secondary particles in atmospheric pollution. The different activity of OC-containing particles might be related to their much smaller aerodynamic diameter. These results could improve our understanding of aerosol characteristics and could be helpful to further investigate the atmospheric process of particles.

  3. Characterization of events by aerosol mass size distributions.

    PubMed

    Nicolás, José; Yubero, Eduardo; Galindo, Nuria; Giménez, Joaquín; Castañer, Ramón; Carratalá, Adoración; Crespo, Javier; Pastor, Carlos

    2009-02-01

    Continuous measurements of particle mass size distributions were carried out in summer 2004 at an urban location in the western Mediterranean using an optical particle counter. In this work we propose a simple methodology to identify PM episodes and determine their influence on mass size distributions. During the study period three types of event produced a significant increase in TSP daily levels: Saharan dust intrusions, firework displays and strong winds, modifying size distributions in different ways. As well, a traffic-related mass size spectrum was obtained showing road dust particles injected into the atmosphere by vehicle-induced resuspension having mainly aerodynamic diameters between 5 and 15 microm. This was confirmed by principal component and conditional probability function analyses.

  4. Evolution of size-segregated aerosol mass concentration during the Antarctic summer at Northern Foothills, Victoria Land

    NASA Astrophysics Data System (ADS)

    Illuminati, Silvia; Bau, Sébastien; Annibaldi, Anna; Mantini, Caterina; Libani, Giulia; Truzzi, Cristina; Scarponi, Giuseppe

    2016-01-01

    Within the framework of the Italian National Programm for Antarctic Research (PNRA), the first direct gravimetric measurements of size-segregated aerosol fractions were carried out at Faraglione Camp, ˜3-km far from the Italian station "M. Zucchelli" (Terra Nova Bay, Ross Sea), during the 2014-2015 austral summer. A six-stage high-volume cascade impactor with size classes between 10 μm and 0.49 μm, and, in parallel, for comparison purposes, a PM10 high-volume sampler (50% cut-off aerodynamic diameter of 10 μm) were used. A 10-day sampling strategy was adopted. Aerosol mass measurements were carried out before and after exposure by using a microbalance specifically designed for the filter weight and placed inside a glove bag in order to maintain stable temperature and humidity conditions during weighing sessions. Measured atmospheric concentrations (referred to the "actual air conditions" of mean temperature of 268 K and mean pressure of 975 hPa) of size-segregated aerosol fractions showed the following values, given as size range, means (interquartile range): Dp < 0.49 μm, 0.33 (0.26-0.34) μg m-3; 0.49-0.95 μm, 0.20 (0.19-0.24) μg m-3; 0.95-1.5 μm, 0.16 (0.13-0.21) μg m-3; 1.5-3.0 μm 0.075 (0.05-0.11) μg m-3; 3.0-7.2 μm 0.12 (0.02-0.19) μg m-3; 7.2-10 μm 0.06 (0.01-0.03) μg m-3. The average mass concentration of the total PM10 at Faraglione Camp for the entire sampling period was 0.92 (0.67-1.1) μg m-3. Although a great variability, the aerosol mass concentration showed a tri-modal distribution, with an accumulation mode (in the range 0.1-1.0 μm) and two coarse modes (CM1 in the range 1.0-3.0 μm, and CM2 in the range 3.0-10 μm). From 50% to 90% of the PM10 mass comes from particles of a size smaller than 1.0 μm. The two coarse modes represented from ˜5% to ˜35% of the PM10, showing opposite seasonal trends (CM1 decreased while CM2 increased). During summer, PM10 mass concentration increased to a maximum of ˜1.6 μg m-3 at mid-December, while

  5. Functional characterization of the water-soluble organic carbon of size fractionated aerosol in the Southern Mississippi Valley

    NASA Astrophysics Data System (ADS)

    Chalbot, M.-C. G.; Brown, J.; Chitranshi, P.; Gamboa da Costa, G.; Pollock, E. D.; Kavouras, I. G.

    2014-02-01

    The chemical content of the water soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to: (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for the period when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5% of particle mass for particles with dp > 0.96 μm and 10% of particle mass for particles with dp < 0.96 μm. Non-exchangeable aliphatic (H-C), unsaturated aliphatic (H-C-C=), oxygenated saturated aliphatic (H-C-O), acetalic (O-CH-O) and aromatic (Ar-H) protons were determined by proton nuclear magnetic resonance. The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m-3 for particles with 0.96 < dp < 1.5 μm to 73.9 ± 12.3 nmol m-3 for particles with dp < 0.49 μm, resulting in molar H / C ratios of 0.48 ± 0.05 to 0.92 ± 0.09 observed in combustion-related organic aerosol. The R-H was the most abundant group representing about 45% of measured total non-exchangeable organic hydrogen concentration followed by H-C-O (27%) and H-C-C= (26%). Levoglucosan, amines, ammonium and methanosulfonate were tentatively identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosol and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from -26.81 ± 0.18‰ for the smallest particles to -25.93 ± 0.31‰ for the largest particles and the relative

  6. Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley

    NASA Astrophysics Data System (ADS)

    Chalbot, M.-C. G.; Brown, J.; Chitranshi, P.; Gamboa da Costa, G.; Pollock, E. D.; Kavouras, I. G.

    2014-06-01

    The chemical content of water-soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for periods when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5% of particle mass for particles with dp > 0.96 μm and 10% of particle mass for particles with dp < 0.96 μm. Non-exchangeable aliphatic (H-C), unsaturated aliphatic (H-C-C=), oxygenated saturated aliphatic (H-C-O), acetalic (O-CH-O) and aromatic (Ar-H) protons were determined by proton nuclear magnetic resonance (1H-NMR). The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m-3 for particles with 1.5 < dp < 3.0 μm to 73.9 ± 12.3 nmol m-3 for particles with dp < 0.49 μm. The molar H / C ratios varied from 0.48 ± 0.05 to 0.92 ± 0.09, which were comparable to those observed for combustion-related organic aerosol. The R-H was the most abundant group, representing about 45% of measured total non-exchangeable organic hydrogen concentrations, followed by H-C-O (27%) and H-C-C= (26%). Levoglucosan, amines, ammonium and methanesulfonate were identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosols and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from -26.81 ± 0.18‰ for the smallest particles to -25.93 ± 0.31‰ for the largest

  7. Three-dimensional factorization of size-resolved organic aerosol mass spectra from Mexico City

    NASA Astrophysics Data System (ADS)

    Ulbrich, I. M.; Canagaratna, M. R.; Cubison, M. J.; Zhang, Q.; Ng, N. L.; Aiken, A. C.; Jimenez, J. L.

    2011-07-01

    A size-resolved submicron organic aerosol composition dataset from a high-resolution time-of-flight mass spectrometer (HR-ToF-AMS) collected in Mexico City during the MILAGRO campaign in March 2006 is analyzed using 3-dimensional (3-D) factorization models. A method for estimating the precision of the size-resolved composition data for use with the factorization models is presented here for the first time. Two 3-D models are applied to the dataset. One model is a 3-vector decomposition (PARAFAC model), which assumes that each chemical component has a constant size distribution over all time steps. The second model is a vector-matrix decomposition (Tucker 1 model) that allows a chemical component to have a size distribution that varies in time. To our knowledge, this is the first report of an application of 3-D factorization models to data from fast aerosol instrumentation; it is also the first application of this vector-matrix model to any ambient aerosol dataset. A larger number of degrees of freedom in the vector-matrix model enable fitting real variations in factor size distributions, but also make the model susceptible to fitting noise in the dataset, giving some unphysical results. For this dataset and model, more physical results were obtained by partially constraining the factor mass spectra using a priori information and a new regularization method. We find four factors with each model: hydrocarbon-like organic aerosol (HOA), biomass-burning organic aerosol (BBOA), oxidized organic aerosol (OOA), and a locally occurring organic aerosol (LOA). These four factors have previously been reported from 2-dimensional factor analysis of the high-resolution mass spectral dataset from this study. The size distributions of these four factors are consistent with previous reports for these particle types. Both 3-D models produce useful results, but the vector-matrix model captures real variability in the size distributions that cannot be captured by the 3-vector model. A

  8. Three-dimensional factorization of size-resolved organic aerosol mass spectra from Mexico City

    NASA Astrophysics Data System (ADS)

    Ulbrich, I. M.; Canagaratna, M. R.; Cubison, M. J.; Zhang, Q.; Ng, N. L.; Aiken, A. C.; Jimenez, J. L.

    2012-01-01

    A size-resolved submicron organic aerosol composition dataset from a high-resolution time-of-flight mass spectrometer (HR-ToF-AMS) collected in Mexico City during the MILAGRO campaign in March 2006 is analyzed using 3-dimensional (3-D) factorization models. A method for estimating the precision of the size-resolved composition data for use with the factorization models is presented here for the first time. Two 3-D models are applied to the dataset. One model is a 3-vector decomposition (PARAFAC model), which assumes that each chemical component has a constant size distribution over all time steps. The second model is a vector-matrix decomposition (Tucker 1 model) that allows a chemical component to have a size distribution that varies in time. To our knowledge, this is the first report of an application of 3-D factorization models to data from fast aerosol instrumentation, and the first application of this vector-matrix model to any ambient aerosol dataset. A larger number of degrees of freedom in the vector-matrix model enable fitting real variations in factor size distributions, but also make the model susceptible to fitting noise in the dataset, giving some unphysical results. For this dataset and model, more physically meaningful results were obtained by partially constraining the factor mass spectra using a priori information and a new regularization method. We find four factors with each model: hydrocarbon-like organic aerosol (HOA), biomass-burning organic aerosol (BBOA), oxidized organic aerosol (OOA), and a locally occurring organic aerosol (LOA). These four factors have previously been reported from 2-dimensional factor analysis of the high-resolution mass spectral dataset from this study. The size distributions of these four factors are consistent with previous reports for these particle types. Both 3-D models produce useful results, but the vector-matrix model captures real variability in the size distributions that cannot be captured by the 3-vector

  9. Quantification of Kras mutant fraction in the lung DNA of mice exposed to aerosolized particulate vanadium pentoxide by inhalation.

    PubMed

    Banda, Malathi; McKim, Karen L; Haber, Lynne T; MacGregor, Judith A; Gollapudi, B Bhaskar; Parsons, Barbara L

    2015-08-01

    This study investigated whether Kras mutation is an early event in the development of lung tumors induced by inhalation of particulate vanadium pentoxide (VP) aerosols. A National Toxicology Program tumor bioassay of inhaled particulate VP aerosols established that VP-induced alveolar/bronchiolar carcinomas of the B6C3F1 mouse lung carried Kras mutations at a higher frequency than observed in spontaneous mouse lung tumors. Therefore, this study sought to: (1) characterize any Kras mutational response with respect to VP exposure concentration, and (2) investigate the possibility that amplification of preexisting Kras mutation is an early event in VP-induced mouse lung tumorigenesis. Male Big Blue B6C3F1 mice (6 mice/group) were exposed to aerosolized particulate VP by inhalation, 6h/day, 5 days/week for 4 or 8 weeks, using VP exposure concentrations of 0, 0.1, and 1 mg/m(3). The levels of two different Kras codon 12 mutations [GGT → GAT (G12D) and GGT → GTT (G12V)] were measured in lung DNAs by Allele-specific Competitive Blocker PCR (ACB-PCR). For both exposure concentrations (0.1 and 1.0mg/m(3)) and both time points (4 and 8 weeks), the mutant fractions observed in VP-exposed mice were not significantly different from the concurrent controls. Given that 8 weeks of inhalation of a tumorigenic concentration of particulate aerosols of VP did not result in a significant change in levels of lung Kras mutation, the data do not support either a direct genotoxic effect of VP on Kras or early amplification of preexisting mutation as being involved in the genesis of VP-induced mouse lung tumors under the exposure conditions used. Rather, the data suggest that accumulation of Kras mutation occurs later with chronic VP exposure and is likely not an early event in VP-induced mouse lung carcinogenesis. PMID:26232258

  10. Aerosol mass spectrometry: particle-vaporizer interactions and their consequences for the measurements

    NASA Astrophysics Data System (ADS)

    Drewnick, F.; Diesch, J.-M.; Faber, P.; Borrmann, S.

    2015-04-01

    The Aerodyne Aerosol Mass Spectrometer (AMS) is a frequently used instrument for on-line measurement of the ambient sub-micron aerosol composition. With the help of calibrations and a number of assumptions on the flash vaporization and electron impact ionization processes this instrument provides robust quantitative information on various ambient aerosol components. However, when measuring close to certain anthropogenic sources or in marine environments, several of these assumptions may not be met and measurement results might easily be misinterpreted. Here we discuss various aspects of the interaction of aerosol particles with the AMS tungsten vaporizer and the consequences for the measurement results: semi-refractory components, i.e. components that vaporize but do not flash vaporize at the vaporizer and ionizer temperatures, like metal halides (e.g. chlorides, bromides or iodides of Al, Ba, Cd, Cu, Fe, Hg, K, Na, Pb, Sr, Zn) can be measured semi-quantitatively despite their relatively slow vaporization from the vaporizer. Even though non-refractory components (e.g. NH4NO3 or (NH4)2SO4) vaporize quickly, their differences in vaporization kinetics can result in undesired biases in ion collection efficiency in the measurements. Chemical reactions with water vapor and oxygen from the aerosol flow can have an influence on the mass spectra for certain components (e.g. NH4NO3, (NH4)2SO4, organic species). Finally, chemical reactions of the aerosol with the vaporizer surface can result in additional signals in the mass spectra (e.g. WO2C2-related signals from particulate Cl) and in conditioning or contamination of the vaporizer with potential memory effects influencing the mass spectra of subsequent measurements. Laboratory experiments that investigate these particle-vaporizer interactions are presented and are discussed together with field results showing that measurements of typical continental or urban aerosols are not significantly affected while laboratory

  11. Outdoor and indoor aerosol size, number, mass and compositional dynamics at an urban background site during warm season

    NASA Astrophysics Data System (ADS)

    Talbot, N.; Kubelova, L.; Makes, O.; Cusack, M.; Ondracek, J.; Vodička, P.; Schwarz, J.; Zdimal, V.

    2016-04-01

    This paper describes the use of a unique valve switching system that allowed for high temporal resolution indoor and outdoor data to be collected concurrently from online C-ToF-AMS, SMPS and OC/EC, and offline BLPI measurements. The results reveal near real-time dynamic aerosol behaviour along a migration path from an outdoor to indoor environment. An outdoor reduction in NR-PM1 mass concentration occurred daily from AM (06:00-12:00) to PM (12:00-18:00). SO4 (26%-37%) [AM/PM] increased proportionally during afternoons at the expense of NO3 (18%-7%). The influences of mixing height, temperature and solar radiation were considered against the mean mass concentration loss for each species. Losses were then calculated according to species via a basic input/output model. NO3 lost the most mass during afternoon periods, which we attribute to the accelerated dissociation of NH4NO3 through increasing temperature and decreasing relative humidity. Indoor/outdoor (I/O) ratios varied from 0.46 for <40 nm to 0.65 for >100 nm. These ratios were calculated using average SMPS PNC measurements over the full campaign and corroborated using a novel technique of calculating I/O penetration ratios through the indoor migration of particles during a new particle formation event. This ratio was then used to observe changes in indoor composition relative to those outdoors. Indoor sampling was carried out in an undisturbed room with no known sources. Indoor concentrations were found to be proportional to those outdoors, with organic matter [2.7 μg/m3] and SO4 [1.7 μg/m3] being the most prominent species. These results are indicative of fairly rapid aerosol penetration, a source-free indoor environment and small afternoon I/O temperature gradients. Fine fraction NO3 was observed indoors in both real-time AMS PM1 and off-line BLPI measurements. Greater mass concentration losses were observed from filter measurements, highlighting an important time dependency factor when investigating semi

  12. Toward new techniques to measure heterogeneous oxidation of aerosol: Electrodynamic Balance-Mass Spectrometry (EDB-MS) and Aerosol X-ray Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Jacobs, M. I.; Heine, N.; Xu, B.; Davies, J. F.; Kirk, B. B.; Kostko, O.; Alayoglu, S.; Wilson, K. R.; Ahmed, M.

    2015-12-01

    The chemical composition and physical properties of aerosol can be changed via heterogeneous oxidation with the OH radical. However, the physical state of the aerosol influences the kinetics of this reaction; liquid particles with a high diffusion coefficient are expected to be well mixed and homogenously oxidized, while oxidation of solid, diffusion-limited aerosol is expected to occur primarily on the surface, creating steep chemical gradients within the particle. We are working to develop several new techniques to study the heterogeneous oxidation of different types of aerosol. We are developing a "modular" electrodynamic balance (EDB) that will enable us to study heterogeneous oxidation at aqueous interfaces using a mass-spectrometer (and potentially other detection techniques). Using a direct analysis in real time (DART) interface, preliminary droplet train measurements have demonstrated single-droplet mass spectrometry to be possible. With long reaction times in our EDB, we will be able to study heterogeneous oxidation of a wide variety of organic species in aqueous droplets. Additionally, we are working to use aerosol photoemission and velocity map imaging (VMI) to study the surface of aerosol particles as they undergo heterogeneous oxidation. With VMI, we're able to collect electrons with a 4π collection efficiency over conventional electron energy analyzers. Preliminary results looking at the ozonolysis of squalene using ultraviolet photoelectron spectroscopy (UPS) show that heterogeneous oxidation kinetic data can be extracted from photoelectron spectra. By moving to X-ray photoemission spectroscopy (XPS), we will determine elemental and chemical composition of the aerosol surface. Thus, aerosol XPS will provide information on the steep chemical gradients that form as diffusion-limited aerosol undergo heterogeneous oxidation.

  13. Characterization of solvent-extractable organics in urban aerosols based on mass spectrum analysis and hygroscopic growth measurement.

    PubMed

    Mihara, Toshiyuki; Mochida, Michihiro

    2011-11-01

    To characterize atmospheric particulate organics with respect to polarity, aerosol samples collected on filters in the urban area of Nagoya, Japan, in 2009 were extracted using water, methanol, and ethyl acetate. The extracts were atomized and analyzed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a hygroscopicity tandem differential mobility analyzer. The atmospheric concentrations of the extracted organics were determined using phthalic acid as a reference material. Comparison of the organic carbon concentrations measured using a carbon analyzer and the HR-ToF-AMS suggests that organics extracted with water (WSOM) and ethyl acetate (EASOM) or those extracted with methanol (MSOM) comprise the greater part of total organics. The oxygen-carbon ratios (O/C) of the extracted organics varied: 0.51-0.75 (WSOM), 0.37-0.48 (MSOM), and 0.27-0.33 (EASOM). In the ion-group analysis, WSOM, MSOM, and EASOM were clearly characterized by the different fractions of the CH and CO(2) groups. On the basis of the hygroscopic growth measurements of the extracts, κ of organics at 90% relative humidity (κ(org)) were estimated. Positive correlation of κ(org) with O/C (r 0.70) was found for MSOM and EASOM, but no clear correlation was found for WSOM.

  14. Characterization of a real-time tracer for Isoprene Epoxydiols-derived Secondary Organic Aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    NASA Astrophysics Data System (ADS)

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

    2015-04-01

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making it the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from

  15. Characterization of a real-time tracer for Isoprene Epoxydiols-derived Secondary Organic Aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    DOE PAGES

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; et al

    2015-04-16

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making itmore » the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA

  16. Real-time measurement of sodium chloride in individual aerosol particles by mass spectrometry

    NASA Technical Reports Server (NTRS)

    Sinha, M. P.; Friedlander, S. K.

    1985-01-01

    The method of particle analysis by mass spectrometry has been applied to the quantitative measurement of sodium chloride in individual particles on a real-time basis. Particles of known masses are individually introduced, in the form of a beam, into a miniature Knudsen cell oven (1600 K). The oven is fabricated from rhenium metal sheet (0.018 mm thick) and is situated in the ion source of a quadrupole mass spectrometer. A particle once inside the oven is trapped and completely volatilized; this overcomes the problem of partial volatilization due to particles bouncing from the filament surface. Individual particles are thermally volatilized and ionized inside the rhenium oven, and produce discrete sodium ion pulses whose intensities are measured with the quadrupole mass spectrometer. An ion pulse width of several milliseconds (4-12 ms) is found for particles in the mass range 1.3 x 10 to the -13th to 5.4 x 10 to the -11th g. The sodium ion intensity is found to be proportional to the particle mass to the 0.86-power. The intensity distribution for monodisperse aerosol particles possesses a geometric standard deviation of 1.09, showing that the method can be used for the determination of the mass distribution function with good resolution in a polydisperse aerosol.

  17. The Development of Electrostatic Precipitation-Electrospray Ionization Mass Spectrometry (EP-ESI-MS) for Atmospheric Aerosol Analysis

    NASA Astrophysics Data System (ADS)

    He, S.; Hogan, C. J., Jr.; Naqwi, A.; Gross, D. S.; Li, L.; Duan, H.; Jiang, L.; Flowers, J.; Grubb, E.; Au, L.

    2015-12-01

    Chemical composition analysis of atmospheric aerosols is of considerable interest and has been facilitated by mass spectrometry. Electrospray ionization (ESI) is a suitable mode of ion generation of many organic species comprising aerosol particles, as it leads to minimal analyte fragmentation. However, particles exist in the atmosphere at mass concentrations of the order 10 μg/m3 or less in many environments and are highly heterogeneous; low concentrations and chemical complexity have limited ESI application in aerosol analysis. In this presentation, the development of an approach to apply ESI to molecules within submicrometer and nanometer scale aerosol particles is discussed. The technique, which we term electrostatic precipitation-ESI-MS (EP-ESI-MS), utilizes unipolar ionization to charge particles, electrostatic precipitation to collect particles on the tip of a tungsten rod, and subsequently, by flowing liquid over the rod, ESI and mass analysis of dissolved species originating from the collected particles. EP-ESI-MS is shown to enable analysis of nanogram quantities of collected inorganic and organic components. Furthermore, it is coupled with a tandem mass spectrometry and challenged with oxidation products of α-pinene to investigate its capability of enabling structure analysis of complex organic compounds in aerosol particles. With EP-ESI-MS, the identification of chemical components in aerosol particles is realized and the integrated mass spectrometric signals are found to be a monotonic function of the analyte mass concentration in the aerosol phase. Additionally, it is shown to have a dynamic range of 5 orders of magnitude in mass, making it suitable for molecular analysis of aerosol particles in laboratory settings, as well as analysis of atmospheric aerosols in ambient air.

  18. Mexico City Aerosol Analysis during MILAGRO using High Resolution Aerosol Mass Spectrometry at the Urban Supersite (T0). Part 1: Fine Particle Composition and Organic Source Apportionment

    SciTech Connect

    Aiken, Allison; Salcedo, D.; Cubison, Michael J.; Huffman, J.; DeCarlo, Peter; Ulbrich, Ingrid M.; Docherty, Kenneth S.; Sueper, D. T.; Kimmel, Joel; Worsnop, Douglas R.; Trimborn, Achim; Northway, Megan; Stone, Elizabeth A.; Schauer, James J.; Volkamer, Rainer M.; Fortner, Edward; de Foy, B.; Wang, Jian; Laskin, Alexander; Shutthanandan, V.; Zheng, Junsheng; Zhang, Renyi; Gaffney, Jeffrey S.; Marley, Nancy A.; Paredes-Miranda, Guadalupe L.; Arnott, W. P.; Molina, Luisa T.; Sosa, G.; Jimenez, Jose L.

    2009-09-11

    Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and complementary instrumentation. Mass concentrations, diurnal cycles, and size distributions of inorganic and organic species are similar to results from the CENICA supersite in April 2003 with organic aerosol (OA) comprising about half of the fine PM mass. Positive Matrix Factorization (PMF) analysis of the high resolution OA spectra identifies three major components: chemically-reduced urban primary emissions (hydrocarbon-like OA, HOA), oxygenated OA (OOA, mostly secondary OA or SOA), and biomass burning OA (BBOA) that correlates with levoglucosan and acetonitrile. BBOA includes several very large plumes from regional fires and likely also some refuse burning.

  19. Submicron particles at Thompson Farm during ICARTT measured using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Cottrell, Laura D.; Griffin, Robert J.; Jimenez, Jose L.; Zhang, Qi; Ulbrich, Ingrid; Ziemba, Luke D.; Beckman, Pieter J.; Sive, Barkley C.; Talbot, Robert W.

    2008-04-01

    The composition and size of aerosols were measured using an Aerodyne quadrupole aerosol mass spectrometer at Thompson Farm in Durham, NH, during the International Consortium for Atmospheric Research on Transport and Transformation campaign during summer 2004. Submicron, non-refractory aerosol was dominated by organic matter and sulfate (averages of 5.7 μg m-3 and 3.6 μg m-3, respectively), with smaller contributions from nitrate and ammonium (averages of 0.3 μg m-3 and 1.02 μg m-3, respectively). Organic aerosol (OA) mass correlates well with anthropogenic tracers such as carbon monoxide (CO, R2 = 0.58) and black carbon (R2 = 0.59), but multiple analyses indicate possible contributions from primary, secondary, anthropogenic, and biogenic OA. Multivariate statistical analysis of the OA mass spectra indicates the presence of two types of oxygenated OA (OOA) and a hydrocarbon-like OA (HOA) component that also contains contributions from biomass burning OA (BBOA). On average, the HOA/BBOA component accounts for 21% of the total OA mass while the two OOA components account for 24% and 55%, respectively, of the OA burden. Observed nitrate correlates well with OA (R2 = 0.67), suggesting interference, the presence of organic nitrates, processing/uptake of nitric acid by OA, or other temporally coincident processes because of the ammonia-poor environment with respect to sulfate. The relative increase of OA with respect to background compared to that of CO (average of 72.7 μg m-3 ppmv-1) indicates values that are higher than those based on previous measurements in New England.

  20. In situ measurements of aerosol mass concentration and radiative properties in Xianghe, southeast of Beijing

    NASA Astrophysics Data System (ADS)

    Chaudhry, Zahra; Martins, J. Vanderlei; Li, Zhanqing; Tsay, Si-Chee; Chen, Hongbin; Wang, Pucai; Wen, Tianxue; Li, Can; Dickerson, Russell R.

    2007-12-01

    As a part of the EAST-AIRE study, Nuclepore filters were collected in two size ranges (coarse, 2.5 μm < d < 10 μm, and fine, d < 2.5 μm) from January to May 2005 in Xianghe, about 70 km southeast of Beijing, and analyzed for aerosol mass concentration, spectral absorption efficiency and absorption coefficient. Twelve-hour aerosol mass concentration measurements showed an average concentration of 120 μg/m3 in the coarse mode and an average concentration of 25 μg/m3 in the fine mode. To determine how representative ground-based measurements are of the total column, the mass concentration data was compared with AERONET AOT at 500 nm and AERONET size distribution data. The vertical distribution of the aerosols were studied with a micropulse lidar and in the cases where the vertical column was found to be fairly homogenous, the comparisons of the filter results with AERONET agreed favorably, while in the cases of inhomogeneity, the comparisons have larger disagreement. For fine mode aerosols, the average spectral absorption efficiency equates well to a λ-1 model, while the coarse mode shows a much flatter spectral dependence, consistent with large particle models. The coarse mode absorption efficiency was compatible with that of the fine mode in the NIR region, indicating the much stronger absorption of the coarse mode due to its composition and sizable mass. Single scattering albedo results are presented from a combination between absorption coefficients derived from the filter measurements, from a PSAP and from a three-wavelength Nephelometer.

  1. Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry.

    PubMed

    Farmer, D K; Matsunaga, A; Docherty, K S; Surratt, J D; Seinfeld, J H; Ziemann, P J; Jimenez, J L

    2010-04-13

    Organonitrates (ON) are important products of gas-phase oxidation of volatile organic compounds in the troposphere; some models predict, and laboratory studies show, the formation of large, multifunctional ON with vapor pressures low enough to partition to the particle phase. Organosulfates (OS) have also been recently detected in secondary organic aerosol. Despite their potential importance, ON and OS remain a nearly unexplored aspect of atmospheric chemistry because few studies have quantified particulate ON or OS in ambient air. We report the response of a high-resolution time-of-flight aerosol mass spectrometer (AMS) to aerosol ON and OS standards and mixtures. We quantify the potentially substantial underestimation of organic aerosol O/C, commonly used as a metric for aging, and N/C. Most of the ON-nitrogen appears as NO(x)+ ions in the AMS, which are typically dominated by inorganic nitrate. Minor organonitrogen ions are observed although their identity and intensity vary between standards. We evaluate the potential for using NO(x)+ fragment ratios, organonitrogen ions, HNO(3)+ ions, the ammonium balance of the nominally inorganic ions, and comparison to ion-chromatography instruments to constrain the concentrations of ON for ambient datasets, and apply these techniques to a field study in Riverside, CA. OS manifests as separate organic and sulfate components in the AMS with minimal organosulfur fragments and little difference in fragmentation from inorganic sulfate. The low thermal stability of ON and OS likely causes similar detection difficulties for other aerosol mass spectrometers using vaporization and/or ionization techniques with similar or larger energy, which has likely led to an underappreciation of these species.

  2. Aerosol formation from high-velocity uranium drops: Comparison of number and mass distributions. Final report

    SciTech Connect

    Rader, D.J.; Benson, D.A.

    1995-05-01

    This report presents the results of an experimental study of the aerosol produced by the combustion of high-velocity molten-uranium droplets produced by the simultaneous heating and electromagnetic launch of uranium wires. These tests are intended to simulate the reduction of high-velocity fragments into aerosol in high-explosive detonations or reactor accidents involving nuclear materials. As reported earlier, the resulting aerosol consists mainly of web-like chain agglomerates. A condensation nucleus counter was used to investigate the decay of the total particle concentration due to coagulation and losses. Number size distributions based on mobility equivalent diameter obtained soon after launch with a Differential Mobility Particle Sizer showed lognormal distributions with an initial count median diameter (CMD) of 0.3 {mu}m and a geometric standard deviation, {sigma}{sub g} of about 2; the CMD was found to increase and {sigma}{sub g} decrease with time due to coagulation. Mass size distributions based on aerodynamic diameter were obtained for the first time with a Microorifice Uniform Deposit Impactor, which showed lognormal distributions with mass median aerodynamic diameters of about 0.5 {mu}m and an aerodynamic geometric standard deviation of about 2. Approximate methods for converting between number and mass distributions and between mobility and aerodynamic equivalent diameters are presented.

  3. Measurements of mesospheric aerosol particles during the ECOMA/MASS campaign 2007.

    NASA Astrophysics Data System (ADS)

    Strelnikova, Irina; Rapp, Markus; Strelnikov, Boris; Latteck, Ralph; Baumgarten, Gerd; Brattli, Alvin; Friedrich, Martin; Gumbel, Jorg; Robertson, Scott

    In August 2007 the joint European-American ECOMA/MASS (Existence and Charge state Of Meteoric smoke particles in the middle Atmosphere/Dust MASS Analyzer) sounding rocket and ground-based campaign took place at the Andøya Rocket Range (ARR) (69° N). This campaign was devoted to the investigation of mesospheric aerosol particles. During this campaign, three instrumented sounding rockets were launched under the PMSE and NLC conditions. All rockets were carrying instruments to characterize mesospheric aerosol particles and their environment. The ECOMA rocket was launched during the first salvo shortly (30 min) after the MASS payload. At that time, the EISCAT (69° N, 19° E) VHF and ALWIN radars observed a double layered PMSE. Also an NLC layer was detected by lidar and photometers onboard each rocket. The main instrument of the ECOMA payload is the "ECOMA particle detector". This instrument comprises a classical Faraday cup with a xenon-flash lamp for the active photoionization/photodetachment of mesospheric smoke particles (MSPs) and the subsequent detection of corresponding photoelectrons. Comparing direct Faraday cup measurements and photocurrents we are able to derive particle properties like number densities and particle radii. We present the results of these measurements that show the presence of aerosol particles inside the NLC and PMSE layer, but not below or above these layers. These results are consistent with model predictions, which account for global transport of meteoric smoke. This implies that ice nucleation in the polar summer needs to be reconsidered.

  4. Thermal desorption single particle mass spectrometry of ambient aerosol in Shanghai

    NASA Astrophysics Data System (ADS)

    Zhai, Jinghao; Wang, Xinning; Li, Jingyan; Xu, Tingting; Chen, Hong; Yang, Xin; Chen, Jianmin

    2015-12-01

    Submicron aerosol volatility, chemical composition, and mixing state were simultaneously measured using a thermodenuder (TD) in-line with a single particle aerosol mass spectrometry (SPAMS) during Nov.12 to Dec. 11 of 2014 in Shanghai. By heating up to 250 °C, the signals of refractory species such as elemental carbon, metallic compounds, and mineral dust in aerosols were enhanced in the mass spectra. At 250 °C, the main particle types present in the size range of 0.2-1.0 μm were biomass burning (37% by number) and elemental carbon (20%). From 1.0 to 2.0 μm, biomass burning (30%), dust (19%) and metal-rich (18%) were the primary particle types. CN- signal remained in the mass spectra of the heated biomass burning particles suggests the existence of some extremely low-volatility nitrogen-containing organics. Laboratory experiments were conducted by burning rice straws, the main source material of biomass burning particles in Southern China, to confirm the less volatile composition contributed by biomass burning. Strong CN- with relative area >0.21 was observed in most of the laboratory-made biomass burning particles when heated above 200 °C and was selected as a new marker to identify the biomass burning particles in the field. The TD-SPAMS measured the size-resolved chemical composition of the individual particle residues at different temperatures and offered more information on the aging processes of primary particles and their sources.

  5. First observation of a mass independent isotopic fractionation in a condensation reaction

    NASA Technical Reports Server (NTRS)

    Thiemens, M. H.; Nelson, R.; Dong, Q. W.; Nuth, Joseph A., III

    1994-01-01

    Thiemens and Heidenreich (1983) first demonstrated that a chemically produced mass independent isotopic fractionation process could produce an isotopic composition which is identical to that observed in Allende inclusions. This raised the possibility that the meteoritic components could be produced by chemical, rather than nuclear processes. In order to develop a mechanistic model of the early solar system, it is important that relevant reactions be studied, particularly, those which may occur in the earliest condensation reactions. The isotopic results for isotopic fractionations associated with condensation processes are reported. A large mass independent isotopic fractionation is observed in one of the experiments.

  6. 40 CFR Table 3 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction.... If a solvent blend matches both the name and CAS number for an entry, that entry's organic HAP...

  7. 40 CFR Table 7 to Subpart Kkkk of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Default Organic HAP Mass Fraction for Petroleum Solvent Groups a 7 Table 7 to Subpart KKKK of Part 63 Protection of Environment ENVIRONMENTAL... Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in...

  8. 40 CFR Table 7 to Subpart Kkkk of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for Petroleum Solvent Groups a 7 Table 7 to Subpart KKKK of Part 63 Protection of Environment ENVIRONMENTAL... Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in...

  9. 40 CFR Table 3 to Subpart Mmmm of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Part 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction.... If a solvent blend matches both the name and CAS number for an entry, that entry's organic HAP...

  10. 40 CFR Table 3 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction.... If a solvent blend matches both the name and CAS number for an entry, that entry's organic HAP...

  11. 40 CFR Table 3 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Default Organic HAP Mass Fraction for... 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction.... If a solvent blend matches both the name and CAS number for an entry, that entry's organic HAP...

  12. 40 CFR Table 7 to Subpart Kkkk of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for Petroleum Solvent Groups a 7 Table 7 to Subpart KKKK of Part 63 Protection of Environment ENVIRONMENTAL... Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in...

  13. 40 CFR Table 3 to Subpart Mmmm of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Part 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction.... If a solvent blend matches both the name and CAS number for an entry, that entry's organic HAP...

  14. 40 CFR Table 3 to Subpart Rrrr of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Metal Furniture Pt. 63, Subpt. RRRR, Table 3 Table 3 to Subpart RRRR of Part 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass fraction values in the following table...

  15. Chemical composition and acidity of size-fractionated inorganic aerosols of 2013-14 winter haze in Shanghai and associated health risk of toxic elements

    NASA Astrophysics Data System (ADS)

    Behera, Sailesh N.; Cheng, Jinping; Huang, Xian; Zhu, Qiongyu; Liu, Ping; Balasubramanian, Rajasekhar

    2015-12-01

    The severe winter haze episode that occurred in Shanghai from December 2013 to January 2014, characterized by elevated levels of particulate matter (PM), received considerable international attention because of its impacts on public health and disruption of day-to-day activities. To examine the characteristics of PM during this haze episode and to assess the chemistry behind formation of secondary inorganic aerosols (SIA) and associated health impacts due to exposure of toxic elements, we characterized eight water soluble inorganic (WSI) ions and twenty four trace elements in twelve size-fractionated PM (10 nm-9.9 μm). The average mass concentrations of coarse (1.8 μm < Dp < 9.9 μm), fine (Dp < 2.5 μm), ultrafine (0.01 μm < Dp < 0.10 μm) and nano (0.01 μm < Dp < 0.056 μm) particles during hazy days were 2.8, 5.2, 5.3 and 5.1 times higher than those during non-hazy days, respectively. The in-situ pH (pHIS), as predicted by the Aerosol Inorganic Model (AIM-IV) in all sizes of PM, was observed to be lower during hazy days (average of -0.64) than that during non-hazy days (average of -0.29); there was an increased acidity in haze aerosols. Based on the measured concentrations of particulate-bound toxic elements, health risk assessment was conducted, which revealed that the excess lifetime carcinogenic risk to individuals exposed to fine particles under haze events increased significantly (P < 0.05) to 69 ± 18 × 10-6 compared to non-hazy days (34 ± 10 × 10-6). The qualitative source attribution analysis suggested that the occurrence of haze could be due to a combination of increased emissions of PM from multiple anthropogenic sources followed by its accumulation under unfavourable meteorological conditions with lower mixing heights and less wind speeds and the formation of secondary aerosols.

  16. Ultrasensitive detection of inhaled organic aerosol particles by accelerator mass spectrometry.

    PubMed

    Parkhomchuk, E V; Gulevich, D G; Taratayko, A I; Baklanov, A M; Selivanova, A V; Trubitsyna, T A; Voronova, I V; Kalinkin, P N; Okunev, A G; Rastigeev, S A; Reznikov, V A; Semeykina, V S; Sashkina, K A; Parkhomchuk, V V

    2016-09-01

    Accelerator mass spectrometry (AMS) was shown to be applicable for studying the penetration of organic aerosols, inhaled by laboratory mice at ultra-low concentration ca. 10(3) cm(-3). We synthesized polystyrene (PS) beads, composed of radiocarbon-labeled styrene, for testing them as model organic aerosols. As a source of radiocarbon we used methyl alcohol with radioactivity. Radiolabeled polystyrene beads were obtained by emulsifier-free emulsion polymerization of synthesized (14)C-styrene initiated by K2S2O8 in aqueous media. Aerosol particles were produced by pneumatic spraying of diluted (14)C-PS latex. Mice inhaled (14)C-PS aerosol consisting of the mix of 10(3) 225-nm particles per 1 cm(3) and 5·10(3) 25-nm particles per 1 cm(3) for 30 min every day during five days. Several millions of 225-nm particles deposited in the lungs and slowly excreted from them during two weeks of postexposure. Penetration of particles matter was also observed for liver, kidneys and brain, but not for a heart. PMID:27281540

  17. Coupled effects of temperature and mass transport on the isotope fractionation of zinc during electroplating

    NASA Astrophysics Data System (ADS)

    Black, Jay R.; John, Seth G.; Kavner, Abby

    2014-01-01

    The isotopic composition of zinc metal electrodeposited on a rotating disc electrode from a Zn-citrate aqueous solution was investigated as a function of overpotential (electrochemical driving force), temperature, and rotation rate. Zn metal was measured to be isotopically light with respect to Zn+2 in solution, with observed fractionations varying from Δ66/64Znmetal-aqueous = -1.0‰ to -3.9‰. Fractionation varies continuously as a function of a dimensionless parameter described by the ratio of observed deposition rate to calculated mass-transport limiting rate, where larger fractionations are observed at lower deposition rates, lower temperature, and at faster electrode rotation rates. Thus, the large fractionation and its rate dependence is interpreted as a competition between the two kinetic processes with different effective activation energies: mass-transport-limited (diffusion limited) kinetics with a large activation energy, which creates small fractionations close to the predicted diffusive fractionation; and electrochemical deposition kinetics, with a smaller effective activation energy, which creates large fractionations at low deposition rates and high hydrodynamic fluxes of solute to the electrode. The results provide a framework for predicting isotope fractionation in processes controlled by two competing reactions with different kinetic isotope effects. Light isotopes are electroplated. In all cases light stable isotopes of the metals are preferentially electroplated, with mass-dependent behavior evident where three or more isotopes are measured. Fractionation is time-independent, meaning that the fractionation factor does not vary with the extent of reaction. In most of our experiments, we have controlled the extent of reaction such that only a small amount of metal is deposited from the stock solution, thus avoiding significant evolution of the reservoir composition. In such experiments, the observed isotope fractionation is constant as a

  18. The dense gas mass fraction of molecular clouds in the Milky Way

    SciTech Connect

    Battisti, Andrew J.; Heyer, Mark H. E-mail: heyer@astro.umass.edu

    2014-01-10

    The mass fraction of dense gas within giant molecular clouds (GMCs) of the Milky Way is investigated using {sup 13}CO data from the Five College Radio Astronomy Observatory Galactic Plane Surveys and the Bolocam Galactic Plane Survey (BGPS) of 1.1 mm dust continuum emission. A sample of 860 compact dust sources are selected from the BGPS catalog and kinematically linked to 344 clouds of extended (>3') {sup 13}CO J = 1-0 emission. Gas masses are tabulated for the full dust source and subregions within the dust sources with mass surface densities greater than 200 M {sub ☉} pc{sup –2}, which are assumed to be regions of enhanced volume density. Masses of the parent GMCs are calculated assuming optically thin {sup 13}CO J = 1-0 emission and local thermodynamic equilibrium conditions. The mean fractional mass of dust sources to host GMC mass is 0.11{sub −0.06}{sup +0.12}. The high column density subregions comprise 0.07{sub −0.05}{sup +0.13} of the mass of the cloud. Owing to our assumptions, these values are upper limits to the true mass fractions. The fractional mass of dense gas is independent of GMC mass and gas surface density. The low dense gas mass fraction suggests that the formation of dense structures within GMCs is the primary bottleneck for star formation. The distribution of velocity differences between the dense gas and the low density material along the line of sight is also examined. We find a strong, centrally peaked distribution centered on zero velocity displacement. This distribution of velocity differences is modeled with radially converging flows toward the dense gas position that are randomly oriented with respect to the observed line of sight. These models constrain the infall velocities to be 2-4 km s{sup –1} for various flow configurations.

  19. Origin and impact of particle-to-particle variations in composition measurements with the nano-aerosol mass spectrometer.

    PubMed

    Klems, Joseph P; Johnston, Murray V

    2013-09-01

    In the nano-aerosol mass spectrometer, individual particles in the 10-30 nm size range are trapped and irradiated with a high pulse energy laser beam. The laser pulse generates a plasma that disintegrates the particle into atomic ions, from which the elemental composition is determined. Particle-to-particle variations among the mass spectra are shown to arise from plasma energetics: Low ionization energy species are enhanced in some spectra while high ionization energy species are enhanced in others. These variations also limit the accuracy and precision of elemental analysis, with higher deviations generally observed when low ionization energy species are dominant in the mass spectrum. For standard datasets generated from nominally identical particles, it is shown that that the error associated with composition measurement is random and that averaging the spectra from a few tens of particles is sufficient for measuring the mole fractions of common elements to within about 10% of the expected value. Averaging a greater number of particles offers limited improvement of the measurement precision but has the deleterious effect of degrading the measurement time-resolution, which is given by the time needed to obtain the required number of particle spectra for averaging. An internally mixed ambient particle dataset was found to give a similar result to the standard datasets, that is, the measured elemental composition converged to the average value after a few tens of particles were averaged.

  20. High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

    SciTech Connect

    Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2015-03-19

    A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents

  1. Monitoring aerosol elemental composition in particle size fractions of long-range transport

    NASA Astrophysics Data System (ADS)

    Metternich, P.; Georgii, H.-W.; Groeneveld, K. O.

    1983-04-01

    Collection of atmospheric samples was performed at Malta, a semi-remote environment in the Mediterranean, in case of long-range transport studies of pollutants and natural substances. Using PIXE as a non-destructive trace-element analytical tool, the elemental composition of these samples was determined. Atmospheric concentrations obtained in this study were of one magnitude higher than those observed over the open North Alantic in purely marine air. For most of the anomalously enriched elements in the Mediterranean aerosol, the high concentrations can be explained by long-range transport.

  2. Aerosol Mass Spectrometry via Laser-Induced Incandescence Particle Vaporization Final Report

    SciTech Connect

    Timothy B. Onasch

    2011-10-20

    We have successfully developed and commercialized a soot particle aerosol mass spectrometer (SP-AMS) instrument to measure mass, size, and chemical information of soot particles in ambient environments. The SP-AMS instrument has been calibrated and extensively tested in the laboratory and during initial field studies. The first instrument paper describing the SP-AMS has been submitted for publication in a peer reviewed journal and there are several related papers covering initial field studies and laboratory studies that are in preparation. We have currently sold 5 SP-AMS instruments (either as complete systems or as SP modules to existing AMS instrument operators).

  3. Chemical Nature Of Titan’s Organic Aerosols Constrained from Spectroscopic and Mass Spectrometric Observations

    NASA Astrophysics Data System (ADS)

    Imanaka, Hiroshi; Cruikshank, D. P.

    2012-10-01

    The Cassini-Huygens observations greately extend our knowledge about Titan’s organic aerosols. The Cassini INMS and CAPS observations clearly demonstrate the formation of large organic molecules in the ionosphere [1, 2]. The VIMS and CIRS instruments have revealed spectral features of the haze covering the mid-IR and far-IR wavelengths [3, 4, 5, 6]. This study attempts to speculate the possible chemical nature of Titan’s aerosols by comparing the currently available observations with our laboratory study. We have conducted a series of cold plasma experiment to investigate the mass spectrometric and spectroscopic properties of laboratory aerosol analogs [7, 8]. Titan tholins and C2H2 plasma polymer are generated with cold plasma irradiations of N2/CH4 and C2H2, respectively. Laser desorption mass spectrum of the C2H2 plasma polymer shows a reasonable match with the CAPS positive ion mass spectrum. Furthermore, spectroscopic features of the the C2H2 plasma polymer in mid-IR and far-IR wavelegths qualitatively show reasonable match with the VIMS and CIRS observations. These results support that the C2H2 plasma polymer is a good candidate material for Titan’s aerosol particles at the altitudes sampled by the observations. We acknowledge funding supports from the NASA Cassini Data Analysis Program, NNX10AF08G, and from the NASA Exobiology Program, NNX09AM95G, and the Cassini Project. [1] Waite et al. (2007) Science 316, 870-875. [2] Crary et al. (2009) Planet. Space Sci. 57, 1847-1856. [3] Bellucci et al. (2009) Icarus 201, 198-216. [4] Anderson and Samuelson (2011) Icarus 212, 762-778. [5] Vinatier et al. (2010) Icarus 210, 852-866. [6] Vinatier et al. (2012) Icarus 219, 5-12. [7] Imanaka et al. (2004) Icarus 168, 344-366. [8] Imanaka et al. (2012) Icarus 218, 247-261.

  4. Molecular Characterization of Biomass Burning Aerosols Using High Resolution Mass Spectrometry

    SciTech Connect

    Smith, Jeffrey S.; Laskin, Alexander; Laskin, Julia

    2009-02-13

    Chemical characterizations of atmospheric aerosols is a serious analytical challenge because of the complexity of particulate matter analyte composed of a large number of compounds with a wide range of molecular structures, physico-chemical properties, and reactivity. In this study chemical composition of biomass burning organic aerosol (BBOA) samples is characterized by high resolution electrospray ionization mass spectrometry (ESI/MS). Accurate mass measurement combined with Kendrick analysis allowed us to assign elemental composition for hundreds of compounds in the range of m/z values of 50-1000. ESI/MS spectra of different BBOA samples contain a variety of distinct, sample specific, characteristic peaks that can be used as unique markers for different types of biofuels. Our results indicate that a significant number of high-MW organic compounds in BBOA samples are highly oxidized polar species that can be efficiently detected using ESI/MS but are difficult to observe using the conventional GCMS analysis of aerosol samples. The average O:C ratios obtained for each of the BBOA samples studied in this work are in a strikingly good agreement with the previously reported values obtained using STXM/NEXAFS. The degree of unsaturation of detected organic compounds shows a clear decrease with increase in the molecular weight of the anyalyte molecules. The decrease is particularly pronounced for the samples containing a large number of CH2-based homologous series.

  5. Chemical characterization of high-molar-mass fractions in a Norway spruce knotwood ethanol extract.

    PubMed

    Smeds, Annika I; Eklund, Patrik C; Willför, Stefan M

    2016-10-01

    The low-molar-mass (LMM) fraction, only, i.e., the GC-eluting compounds, which are mainly lignans, has been characterized in Norway spruce knotwood hydrophilic extracts previously. Of this fraction, many lignans and sesquilignans and all GC peaks supposedly representing dilignans remain unidentified. In this work, dilignans and the GC non-eluting compounds (the high-molar mass fractions, HMM) were characterized in a 7-hydroxymatairesinol-reduced knotwood ethanol extract of Norway spruce by using several fractionation and analytical techniques. A methyl tert-butyl ether (MTBE) insoluble fraction of the extract contained mainly HMM material, of which the main part was shown to consist of lignan oligomers. The oligolignans (with a molar mass up to approximately 3700 Da) seemed to be linked by 55' bonds, some of them containing one or two guaiacylglycerol ether units linked to the lignan by βO4 or β5 bonds. Several oligolignans were identified or tentatively identified. The MTBE soluble fraction, which accounted for the major part (81%) of the extract, contained mainly LMM material (lignans, sesqui- and dilignans). The part of the HMM material in the MTBE soluble fraction that was easily isolable (2%) seemed to contain polymers of fatty acids and alcohols, resin acids, and sterols. PMID:27256310

  6. Stable isotope ratio measurements of Cu and Zn in mineral dust (bulk and size fractions) from the Taklimakan Desert and the Sahel and in aerosols from the eastern tropical North Atlantic Ocean.

    PubMed

    Dong, Shuofei; Weiss, Dominik J; Strekopytov, Stanislav; Kreissig, Katharina; Sun, Youbin; Baker, Alex R; Formenti, Paola

    2013-09-30

    Accurate characterization of the stable isotope composition of Cu and Zn in major global mineral dust sources and in aerosols is central to the application of these isotope systems to the studies of global geochemical processes and cycles. We test here for the first time Cu and Zn isotope ratios within a well-defined source-receptor setting on the continent-ocean interface and determine the isotope composition of (i) bulk surface soil dust samples from the Sahel region, (ii) individual size fractions of surface dust samples from the Taklimakan Desert, and (iii) aerosols collected in the equatorial eastern North Atlantic region. This is achieved reducing the blank contribution during the ion exchange step using small resin and acid volumes and using a second ion exchange passage to purify the Cu fraction. We find no significant correlation between size fractions and isotope ratios in the two samples analyzed from the Taklimakan Desert. Mass balance calculations suggest that isotope ratios of bulk samples are within the analytical precision of the <4 μm size fraction and can be used to characterize atmospheric long range transport of Cu and Zn in mineral dust from the Taklimakan Desert. The <1 µm size fractions of two aerosol samples collected over the equatorial eastern North Atlantic region have Cu and Zn isotope ratios that are different to Sahel surface soil dust suggesting important non-crustal sources, in line with calculated enrichment factors, and possibly of anthropogenic origin. Using previously reported δ(66)Zn values for anthropogenic emission from Europe, preliminary calculations suggest that up to 55% of Zn arriving at the sampling points in the equatorial eastern North Atlantic region could be of anthropogenic origin.

  7. Development of Soft Ionization for Particulate Organic Detection with the Aerodyne Aerosol Mass Spectrometer

    SciTech Connect

    Trimborn, A; Williams, L R; Jayne, J T; Worsnop, D R

    2008-06-19

    During this DOE SBIR Phase II project, we have successfully developed several soft ionization techniques, i.e., ionization schemes which involve less fragmentation of the ions, for use with the Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS). Vacuum ultraviolet single photon ionization was demonstrated in the laboratory and deployed in field campaigns. Vacuum ultraviolet single photon ionization allows better identification of organic species in aerosol particles as shown in laboratory experiments on single component particles, and in field measurements on complex multi-component particles. Dissociative electron attachment with lower energy electrons (less than 30 eV) was demonstrated in the measurement of particulate organics in chamber experiments in Switzerland, and is now a routine approach with AMS systems configured for bipolar, negative ion detection. This technique is particularly powerful for detection of acidic and other highly oxygenated secondary organic aerosol (SOA) chemical functionality. Low energy electron ionization (10 to 12 eV) is also a softer ionization approach routinely available to AMS users. Finally, Lithium ion attachment has been shown to be sensitive to more alkyl-like chemical functionality in SOA. Results from Mexico City are particularly exciting in observing changes in SOA molecular composition under different photochemical/meteorological conditions. More recent results detecting biomass burns at the Montana fire lab have demonstrated quantitative and selective detection of levoglucosan. These soft ionization techniques provide the ToF-AMS with better capability for identifying organic species in ambient atmospheric aerosol particles. This, in turn, will allow more detailed study of the sources, transformations and fate of organic-containing aerosol.

  8. Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants.

    PubMed

    Martin, Audrey N; Farquar, George R; Frank, Matthias; Gard, Eric E; Fergenson, David P

    2007-08-15

    Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs. PMID:17630721

  9. Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants.

    PubMed

    Martin, Audrey N; Farquar, George R; Frank, Matthias; Gard, Eric E; Fergenson, David P

    2007-08-15

    Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs.

  10. Evolution of wavelength-dependent mass absorption cross sections of carbonaceous aerosols during the 2010 DOE CARES campaign

    NASA Astrophysics Data System (ADS)

    Flowers, B. A.; Dubey, M. K.; Subramanian, R.; Sedlacek, A. J.; Kelley, P.; Luke, W. T.; Jobson, B. T.; Zaveri, R. A.

    2011-12-01

    Predictions of aerosol radiative forcing require process level optical property models that are built on precise and accurate field observations. Evolution of aerosol optical properties for urban influenced carbonaceous aerosol undergoing transport and mixing with rural air masses was a focal point of the DOE Carbonaceous Aerosol and Radiative Effects (CARES) campaign near Sacramento, CA in summer 2010. Urban aerosol was transported from Sacramento, CA (T0) to the foothills of the Sierra Nevada Mountains to a rural site located near Cool, CA (T1). Aerosol absorption and scattering coefficients were measured at the T0 and T1 sites using integrated photoacoustic acoustic/nephelometer instruments (PASS-3 and PASS-UV) at 781, 532, 405, and 375 nm. Single particle soot photometry (SP2) instrumentation was used to monitor black carbon (BC) mass at both sites. Combining data from these sensors allows estimate of the wavelength-dependent mass absorption coefficient (MAC(λ)) and partitioning of MAC(λ) into contributions from the BC core and from enhancements from coating of BC cores. MAC(λ) measured in this way is free of artifacts associated with filter-based aerosol absorption measurements and takes advantage of the single particle sensitivity of the SP2 instrument, allowing observation of MAC(λ) on 10 minute and faster time scales. Coating was observed to enhance MAC(λ) by 20 - 30 % and different wavelength dependence for MAC(λ) was observed for urban and biomass burning aerosol. Further, T0 - T1 evolution of MAC(λ) was correlated with separately measured NO/NOy ratios and CO/CO2 ratios to understand the effects of aging & transport on MAC(λ) and the implications of aerosol processing that links air quality to radiative forcing on a regional scale. Aircraft observations made from the Gulfstream-1 during CARES are also analyzed to enhance process level understanding of the optical properties of fresh and aged carbonaceous aerosol in the urban-rural interface.

  11. Sugars in Antarctic aerosol

    NASA Astrophysics Data System (ADS)

    Barbaro, Elena; Kirchgeorg, Torben; Zangrando, Roberta; Vecchiato, Marco; Piazza, Rossano; Barbante, Carlo; Gambaro, Andrea

    2015-10-01

    The processes and transformations occurring in the Antarctic aerosol during atmospheric transport were described using selected sugars as source tracers. Monosaccharides (arabinose, fructose, galactose, glucose, mannose, ribose, xylose), disaccharides (sucrose, lactose, maltose, lactulose), alcohol-sugars (erythritol, mannitol, ribitol, sorbitol, xylitol, maltitol, galactitol) and anhydrosugars (levoglucosan, mannosan and galactosan) were measured in the Antarctic aerosol collected during four different sampling campaigns. For quantification, a sensitive high-pressure anion exchange chromatography was coupled with a single quadrupole mass spectrometer. The method was validated, showing good accuracy and low method quantification limits. This study describes the first determination of sugars in the Antarctic aerosol. The total mean concentration of sugars in the aerosol collected at the "Mario Zucchelli" coastal station was 140 pg m-3; as for the aerosol collected over the Antarctic plateau during two consecutive sampling campaigns, the concentration amounted to 440 and 438 pg m-3. The study of particle-size distribution allowed us to identify the natural emission from spores or from sea-spray as the main sources of sugars in the coastal area. The enrichment of sugars in the fine fraction of the aerosol collected on the Antarctic plateau is due to the degradation of particles during long-range atmospheric transport. The composition of sugars in the coarse fraction was also investigated in the aerosol collected during the oceanographic cruise.

  12. Coupled effects of temperature and mass transport on the isotope fractionation of zinc during electroplating

    NASA Astrophysics Data System (ADS)

    Black, Jay R.; John, Seth G.; Kavner, Abby

    2014-01-01

    The isotopic composition of zinc metal electrodeposited on a rotating disc electrode from a Zn-citrate aqueous solution was investigated as a function of overpotential (electrochemical driving force), temperature, and rotation rate. Zn metal was measured to be isotopically light with respect to Zn+2 in solution, with observed fractionations varying from Δ66/64Znmetal-aqueous = -1.0‰ to -3.9‰. Fractionation varies continuously as a function of a dimensionless parameter described by the ratio of observed deposition rate to calculated mass-transport limiting rate, where larger fractionations are observed at lower deposition rates, lower temperature, and at faster electrode rotation rates. Thus, the large fractionation and its rate dependence is interpreted as a competition between the two kinetic processes with different effective activation energies: mass-transport-limited (diffusion limited) kinetics with a large activation energy, which creates small fractionations close to the predicted diffusive fractionation; and electrochemical deposition kinetics, with a smaller effective activation energy, which creates large fractionations at low deposition rates and high hydrodynamic fluxes of solute to the electrode. The results provide a framework for predicting isotope fractionation in processes controlled by two competing reactions with different kinetic isotope effects. Light isotopes are electroplated. In all cases light stable isotopes of the metals are preferentially electroplated, with mass-dependent behavior evident where three or more isotopes are measured. Fractionation is time-independent, meaning that the fractionation factor does not vary with the extent of reaction. In most of our experiments, we have controlled the extent of reaction such that only a small amount of metal is deposited from the stock solution, thus avoiding significant evolution of the reservoir composition. In such experiments, the observed isotope fractionation is constant as a

  13. Model-based evaluation of microbial mass fractions: effect of absolute anaerobic reaction time on microbial mass fractions.

    PubMed

    Tunçal, Tolga

    2010-04-14

    Although enhanced biological phosphorus removal processes (EBPR) are popular methods for nutrient control, unstable treatment performances of full-scale systems are still not well understood. In this study, the interaction between electron acceptors present at the start of the anaerobic phase of an EBPR system and the amount of organic acids generated from simple substrate (rbsCOD) was investigated in a full-scale wastewater treatment plant. Quantification of microbial groups including phosphorus-accumulating microorganisms (PAOs), denitrifying PAOs (DPAOs), glycogen-accumulating microorganisms (GAOs) and ordinary heterotrophic microorganisms (OHOs) was based on a modified dynamic model. The intracellular phosphorus content of PAOs was also determined by the execution of mass balances for the biological stages of the plant. The EBPR activities observed in the plant and in batch tests (under idealized conditions) were compared with each other statistically as well. Modelling efforts indicated that the use of absolute anaerobic reaction (eta1) instead of nominal anaerobic reaction time (eta), to estimate the amount of available substrate for PAOs, significantly improved model accuracy. Another interesting result of the study was the differences in EBPR characteristics observed in idealized and real conditions. PMID:20480829

  14. 40 CFR Table 4 to Subpart Rrrr of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups 1

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Metal Furniture Pt. 63, Subpt. RRRR, Table 4 Table 4 to Subpart RRRR of Part 63—Default Organic HAP Mass... Average organic HAP mass fraction Typical organic percent HAP, by mass Aliphatic 2 0.03 1% Xylene,...

  15. 40 CFR Table 6 to Subpart Kkkk of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Metal Cans Pt. 63, Subpt. KKKK, Table 6 Table 6 to Subpart KKKK of Part 63—Default Organic HAP Mass... blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP, percent by mass 1. Toluene...

  16. 40 CFR Table 3 to Subpart Rrrr of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Metal Furniture Pt. 63, Subpt. RRRR, Table 3 Table 3 to Subpart RRRR of Part 63—Default Organic HAP Mass... blend CAS. No. Average organic HAP mass fraction Typical organic HAP, percent by mass 1. Toluene...

  17. 40 CFR Table 6 to Subpart Kkkk of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Metal Cans Pt. 63, Subpt. KKKK, Table 6 Table 6 to Subpart KKKK of Part 63—Default Organic HAP Mass... blend CAS. No. Averageorganic HAP mass fraction Typical organic HAP, percent by mass 1. Toluene...

  18. Eddy covariance measurements with high-resolution time-of-flight aerosol mass spectrometry: a new approach to chemically-resolved aerosol fluxes

    NASA Astrophysics Data System (ADS)

    Farmer, D. K.; Kimmel, J. R.; Phillips, G.; Docherty, K. S.; Worsnop, D. R.; Sueper, D.; Nemitz, E.; Jimenez, J. L.

    2010-12-01

    Although laboratory studies show that biogenic volatile organic compounds (VOCs) yield substantial secondary organic aerosol (SOA), production of biogenic SOA as indicated by upward fluxes has not been conclusively observed over forests. Further, while aerosols are known to deposit to surfaces, few techniques exist to provide chemically-resolved particle deposition fluxes. To better constrain aerosol sources and sinks, we have developed a new technique to directly measure fluxes of chemically-resolved submicron aerosols using the high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) in a new, fast eddy covariance mode. This approach takes advantage of the instrument's ability to quantitatively identify both organic and inorganic components, including ammonium, sulphate and nitrate, at a temporal resolution of several Hz. The new approach has been successfully deployed over a temperate ponderosa pine plantation in California during the BEARPEX-2007 campaign, providing both total and chemically resolved non-refractory (NR) PM1 fluxes. Average deposition velocity for total NR-PM1 aerosol at noon was 2.05 ± 0.04 mm/s. Using a high resolution measurement of the NH2+ and NH3+ fragments, we demonstrate the first eddy covariance flux measurements of particulate ammonium, which show a noon-time deposition velocity of 1.9 ± 0.7 mm/s and are dominated by deposition of ammonium sulphate.

  19. Eddy covariance measurements with high-resolution time-of-flight aerosol mass spectrometry: a new approach to chemically resolved aerosol fluxes

    NASA Astrophysics Data System (ADS)

    Farmer, D. K.; Kimmel, J. R.; Phillips, G.; Docherty, K. S.; Worsnop, D. R.; Sueper, D.; Nemitz, E.; Jimenez, J. L.

    2011-06-01

    Although laboratory studies show that biogenic volatile organic compounds (VOCs) yield substantial secondary organic aerosol (SOA), production of biogenic SOA as indicated by upward fluxes has not been conclusively observed over forests. Further, while aerosols are known to deposit to surfaces, few techniques exist to provide chemically-resolved particle deposition fluxes. To better constrain aerosol sources and sinks, we have developed a new technique to directly measure fluxes of chemically-resolved submicron aerosols using the high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) in a new, fast eddy covariance mode. This approach takes advantage of the instrument's ability to quantitatively identify both organic and inorganic components, including ammonium, sulphate and nitrate, at a temporal resolution of several Hz. The new approach has been successfully deployed over a temperate ponderosa pine plantation in California during the BEARPEX-2007 campaign, providing both total and chemically resolved non-refractory (NR) PM1 fluxes. Average deposition velocities for total NR-PM1 aerosol at noon were 2.05 ± 0.04 mm s-1. Using a high resolution measurement of the NH2+ and NH3+ fragments, we demonstrate the first eddy covariance flux measurements of particulate ammonium, which show a noon-time deposition velocity of 1.9 ± 0.7 mm s-1 and are dominated by deposition of ammonium sulphate.

  20. Fractional iron solubility of aerosol particles enhanced by biomass burning and ship emission in Shanghai, East China.

    PubMed

    Fu, H B; Shang, G F; Lin, J; Hu, Y J; Hu, Q Q; Guo, L; Zhang, Y C; Chen, J M

    2014-05-15

    In terms of understanding Fe mobilization from aerosol particles in East China, the PM2.5 particles were collected in spring at Shanghai. Combined with the backtrajectory analysis, the PM2.5/PM10 and Ca/Al ratios, a serious dust-storm episode (DSE) during the sampling was identified. The single-particle analysis showed that the major iron-bearing class is the aluminosilicate dust during DSE, while the Fe-bearing aerosols are dominated by coal fly ash, followed by a minority of iron oxides during the non-dust storm days (NDS). Chemical analyses of samples showed that the fractional Fe solubility (%FeS) is much higher during NDS than that during DSE, and a strong inverse relationship of R(2)=0.967 between %FeS and total atmospheric iron loading were found, suggested that total Fe (FeT) is not controlling soluble Fe (FeS) during the sampling. Furthermore, no relationship between FeS and any of acidic species was established, suggesting that acidic process on aerosol surfaces are not involved in the trend of iron solubility. It was thus proposed that the source-dependent composition of aerosol particles is a primary determinant for %FeS. Specially, the Al/Fe ratio is poorly correlated (R(2)=0.113) with %FeS, while the apparent relationship between %FeS and the calculated KBB(+)/Fe ratio (R(2)=0.888) and the V/Fe ratio (R(2)=0.736) were observed, reflecting that %FeS could be controlled by both biomass burning and oil ash from ship emission, rather than mineral particles and coal fly ash, although the latter two are the main contributors to the atmospheric Fe loading during the sampling. Such information can be useful improving our understanding on iron solubility on East China, which may further correlate with iron bioavailability to the ocean, as well as human health effects associated with exposure to fine Fe-rich particles in densely populated metropolis in China. PMID:24607631

  1. Fractional iron solubility of aerosol particles enhanced by biomass burning and ship emission in Shanghai, East China.

    PubMed

    Fu, H B; Shang, G F; Lin, J; Hu, Y J; Hu, Q Q; Guo, L; Zhang, Y C; Chen, J M

    2014-05-15

    In terms of understanding Fe mobilization from aerosol particles in East China, the PM2.5 particles were collected in spring at Shanghai. Combined with the backtrajectory analysis, the PM2.5/PM10 and Ca/Al ratios, a serious dust-storm episode (DSE) during the sampling was identified. The single-particle analysis showed that the major iron-bearing class is the aluminosilicate dust during DSE, while the Fe-bearing aerosols are dominated by coal fly ash, followed by a minority of iron oxides during the non-dust storm days (NDS). Chemical analyses of samples showed that the fractional Fe solubility (%FeS) is much higher during NDS than that during DSE, and a strong inverse relationship of R(2)=0.967 between %FeS and total atmospheric iron loading were found, suggested that total Fe (FeT) is not controlling soluble Fe (FeS) during the sampling. Furthermore, no relationship between FeS and any of acidic species was established, suggesting that acidic process on aerosol surfaces are not involved in the trend of iron solubility. It was thus proposed that the source-dependent composition of aerosol particles is a primary determinant for %FeS. Specially, the Al/Fe ratio is poorly correlated (R(2)=0.113) with %FeS, while the apparent relationship between %FeS and the calculated KBB(+)/Fe ratio (R(2)=0.888) and the V/Fe ratio (R(2)=0.736) were observed, reflecting that %FeS could be controlled by both biomass burning and oil ash from ship emission, rather than mineral particles and coal fly ash, although the latter two are the main contributors to the atmospheric Fe loading during the sampling. Such information can be useful improving our understanding on iron solubility on East China, which may further correlate with iron bioavailability to the ocean, as well as human health effects associated with exposure to fine Fe-rich particles in densely populated metropolis in China.

  2. Modal structure of chemical mass size distribution in the high Arctic aerosol

    NASA Astrophysics Data System (ADS)

    Hillamo, Risto; Kerminen, Veli-Matti; Aurela, Minna; MäKelä, Timo; Maenhaut, Willy; Leek, Caroline

    2001-11-01

    Chemical mass size distributions of aerosol particles were measured in the remote marine boundary layer over the central Arctic Ocean as part of the Atmospheric Research Program on the Arctic Ocean Expedition 1996 (AOE-96). An inertial impaction method was used to classify aerosol particles into different size classes for subsequent chemical analysis. The particle chemical composition was determined by ion chromatography and by the particle-induced X-ray emission technique. Continuous particle size spectra were extracted from the raw data using a data inversion method. Clear and varying modal structures for aerosols consisting of primary sea-salt particles or of secondary particles related to dimethyl sulfide emissions were found. Concentration levels of all modes decreased rapidly when the distance from open sea increased. In the submicrometer size range the major ions found by ion chromatography were sulfate, methane sulfonate, and ammonium. They had most of the time a clear Aitken mode and one or two accumulation modes, with aerodynamic mass median diameters around 0.1 μm, 0.3 μm, and between 0.5-1.0 μm, respectively. The overall submicron size distributions of these three ions were quite similar, suggesting that they were internally mixed over most of this size range. The corresponding modal structure was consistent with the mass size distributions derived from the particle number size distributions measured with a differential mobility particle sizer. The Aitken to accumulation mode mass ratio for nss-sulfate and MSA was substantially higher during clear skies than during cloudy periods. Primary sea-salt particles formed a mode with an aerodynamic mass median diameter around 2 μm. In general, the resulting continuous mass size distributions displayed a clear modal structure consistent with our understanding of the two known major source mechanisms. One is the sea-salt aerosol emerging from seawater by bubble bursting. The other is related to

  3. Demonstration of a VUV lamp photoionization source for improvedorganic speciation in an aerosol mass spectrometer

    SciTech Connect

    Northway, M.J.; Jayne, J.T.; Toohey, D.W.; Canagaratna, M.R.; Trimborn, A.; Akiyama, K-I.; Shimono, A.; Jimenez, J.L.; DeCarlo, P.F.; Wilson, K.R.; Worsnop, D.R.

    2007-10-03

    In recent years, the Aerodyne AerosolMass Spectrometer(AMS) has become a widely used tool for determining aerosol sizedistributions and chemical composition for non-refractory inorganic andorganic aerosol. The current version of the AMS uses a combination offlash thermal vaporization and 70 eV electron impact (EI) ionization.However, EI causes extensive fragmentation and mass spectra of organicaerosols are difficult to deconvolute because they are composites of theoverlapping fragmentation patterns of all species present. Previous AMSstudies have been limited to classifying organics in broad categoriessuch as oxidized and hydrocarbon-like." In this manuscript we present newefforts to gain more information about organic aerosol composition byemploying the softer technique of vacuum ultraviolet (VUV) ionization ina Time-of-Flight AMS (ToF-AMS). In our novel design a VUV lamp is placedin direct proximity of the ionization region of the AMS, with only awindow separating the lamp and the ionizer. This design allows foralternation of photoionization and electron impact ionization within thesame instrument on the timescale of minutes. Thus, the EI-basedquantification capability of the AMS is retained while improved spectralinterpretation is made possible by combined analysis of the complementaryVUV and EI ionization spectra. Photoionization and electron impactionization spectra are compared for a number of compounds including oleicacid, long chain hydrocarbons, and cigarette smoke. In general, the VUVspectra contain much less fragmentation than the EI spectra and for manycompounds the parent ion is the dominant ion in the VUV spectrum. As anexample of the usefulness of the integration of PI within the fullcapability of the ToF-AMS, size distributions and size-segregated massspectra are examined for the cigarette smoke analysis. As a finalevaluation of the new VUV module, spectra for oleic acid are compared tosimilar experiments conducted using the tunable VUV radiation

  4. Multiday production of condensing organic aerosol mass in urban and forest outflow

    DOE PAGES

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.; Camredon, M.; Valorso, R.

    2015-01-16

    Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for multiple days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (~50%) and of shorter duration (1–2 days). The multiday production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction productsmore » of both aromatics and alkanes, especially those with relatively low carbon numbers (C4–15). In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions and different vapor pressure schemes, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

  5. Multiday production of condensing organic aerosol mass in urban and forest outflow

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.; Camredon, M.; Valorso, R.

    2014-07-01

    Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for several days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (∼50%) and of shorter duration (1-2 days). The production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction products of both aromatics and alkanes. In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.

  6. Multiday production of condensing organic aerosol mass in urban and forest outflow

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.; Camredon, M.; Valorso, R.

    2015-01-01

    Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for multiple days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (~50%) and of shorter duration (1-2 days). The multiday production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction products of both aromatics and alkanes, especially those with relatively low carbon numbers (C4-15). In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions and different vapor pressure schemes, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.

  7. Multiday production of condensing organic aerosol mass in urban and forest outflow

    DOE PAGES

    Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.; Camredon, M.; Valorso, R.

    2014-07-03

    Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for several days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (∼50%) and of shorter duration (1–2 days). The production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction products ofmore » both aromatics and alkanes. In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

  8. Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley

    PubMed Central

    Chalbot, M.-C. G.; Brown, J.; Chitranshi, P.; da Costa, G. Gamboa; Pollock, E. D.; Kavouras, I. G.

    2016-01-01

    The chemical content of water-soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for periods when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5 % of particle mass for particles with δp > 0.96 μm and 10 % of particle mass for particles with δp < 0.96 μm. Non-exchangeable aliphatic (H–C), unsaturated aliphatic (H–C–C=), oxygenated saturated aliphatic (H–C–O), acetalic (O–CH–O) and aromatic (Ar–H) protons were determined by proton nuclear magnetic resonance (1H-NMR). The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m−3 for particles with 1.5 < δp < 3.0 μm to 73.9 ± 12.3 nmol m−3 for particles with δp < 0.49 μm. The molar H/C ratios varied from 0.48 ± 0.05 to 0.92 ± 0.09, which were comparable to those observed for combustion-related organic aerosol. The R–H was the most abundant group, representing about 45 % of measured total non-exchangeable organic hydrogen concentrations, followed by H–C–O (27 %) and H–C–C= (26 %). Levoglucosan, amines, ammonium and methanesulfonate were identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosols and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from −26.81 ± 0.18 ‰ for the smallest particles to

  9. Isotope mass fractionation during evaporation of Mg2SiO4

    NASA Technical Reports Server (NTRS)

    Davis, Andrew M.; Clayton, Robert N.; Mayeda, Toshiko K.; Hashimoto, Akihiko

    1990-01-01

    Synthetic forsterite (Mg2SiO4) was partially evaporated in vacuum for various durations and at different temperatures. The residual charges obtained when molten Mg2SiO4 was evaporated to 12 percent of its initial mass were enriched in heavy isotopes by about 20, 30, and 15 per mil/amu for O, Mg, and Si, respectively, whereas solid forsterite evaporated to a similar residual mass fraction showed negligible fractionations. These results imply that calcium and aluminum-rich refractory inclusions in carbonaceous chondrites must have been at least partially molten in the primordial solar nebula if the observed large mass fractionation effects were caused by evaporation processes in the nebula.

  10. Aerosol characterization over the southeastern United States using high-resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition and sources with a focus on organic nitrates

    NASA Astrophysics Data System (ADS)

    Xu, L.; Suresh, S.; Guo, H.; Weber, R. J.; Ng, N. L.

    2015-07-01

    We deployed a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) to characterize the chemical composition of submicron non-refractory particulate matter (NR-PM1) in the southeastern USA. Measurements were performed in both rural and urban sites in the greater Atlanta area, Georgia (GA), and Centreville, Alabama (AL), for approximately 1 year as part of Southeastern Center for Air Pollution and Epidemiology study (SCAPE) and Southern Oxidant and Aerosol Study (SOAS). Organic aerosol (OA) accounts for more than half of NR-PM1 mass concentration regardless of sampling sites and seasons. Positive matrix factorization (PMF) analysis of HR-ToF-AMS measurements identified various OA sources, depending on location and season. Hydrocarbon-like OA (HOA) and cooking OA (COA) have important, but not dominant, contributions to total OA in urban sites (i.e., 21-38 % of total OA depending on site and season). Biomass burning OA (BBOA) concentration shows a distinct seasonal variation with a larger enhancement in winter than summer. We find a good correlation between BBOA and brown carbon, indicating biomass burning is an important source for brown carbon, although an additional, unidentified brown carbon source is likely present at the rural Yorkville site. Isoprene-derived OA factor (isoprene-OA) is only deconvolved in warmer months and contributes 18-36 % of total OA. The presence of isoprene-OA factor in urban sites is more likely from local production in the presence of NOx than transport from rural sites. More-oxidized and less-oxidized oxygenated organic aerosol (MO-OOA and LO-OOA, respectively) are dominant fractions (47-79 %) of OA in all sites. MO-OOA correlates well with ozone in summer but not in winter, indicating MO-OOA sources may vary with seasons. LO-OOA, which reaches a daily maximum at night, correlates better with estimated nitrate functionality from organic nitrates than total nitrates. Based

  11. Particulate matter beyond mass: recent health evidence on the role of fractions, chemical constituents and sources of emission.

    PubMed

    Cassee, Flemming R; Héroux, Marie-Eve; Gerlofs-Nijland, Miriam E; Kelly, Frank J

    2013-12-01

    Particulate matter (PM) is regulated in various parts of the world based on specific size cut offs, often expressed as 10 or 2.5 µm mass median aerodynamic diameter. This pollutant is deemed one of the most dangerous to health and moreover, problems persist with high ambient concentrations. Continuing pressure to re-evaluate ambient air quality standards stems from research that not only has identified effects at low levels of PM but which also has revealed that reductions in certain components, sources and size fractions may best protect public health. Considerable amount of published information have emerged from toxicological research in recent years. Accumulating evidence has identified additional air quality metrics (e.g. black carbon, secondary organic and inorganic aerosols) that may be valuable in evaluating the health risks of, for example, primary combustion particles from traffic emissions, which are not fully taken into account with PM2.5 mass. Most of the evidence accumulated so far is for an adverse effect on health of carbonaceous material from traffic. Traffic-generated dust, including road, brake and tire wear, also contribute to the adverse effects on health. Exposure durations from a few minutes up to a year have been linked with adverse effects. The new evidence collected supports the scientific conclusions of the World Health Organization Air Quality Guidelines and also provides scientific arguments for taking decisive actions to improve air quality and reduce the global burden of disease associated with air pollution.

  12. Particulate matter beyond mass: recent health evidence on the role of fractions, chemical constituents and sources of emission

    PubMed Central

    Héroux, Marie-Eve; Gerlofs-Nijland, Miriam E.; Kelly, Frank J.

    2013-01-01

    Particulate matter (PM) is regulated in various parts of the world based on specific size cut offs, often expressed as 10 or 2.5 µm mass median aerodynamic diameter. This pollutant is deemed one of the most dangerous to health and moreover, problems persist with high ambient concentrations. Continuing pressure to re-evaluate ambient air quality standards stems from research that not only has identified effects at low levels of PM but which also has revealed that reductions in certain components, sources and size fractions may best protect public health. Considerable amount of published information have emerged from toxicological research in recent years. Accumulating evidence has identified additional air quality metrics (e.g. black carbon, secondary organic and inorganic aerosols) that may be valuable in evaluating the health risks of, for example, primary combustion particles from traffic emissions, which are not fully taken into account with PM2.5 mass. Most of the evidence accumulated so far is for an adverse effect on health of carbonaceous material from traffic. Traffic-generated dust, including road, brake and tire wear, also contribute to the adverse effects on health. Exposure durations from a few minutes up to a year have been linked with adverse effects. The new evidence collected supports the scientific conclusions of the World Health Organization Air Quality Guidelines and also provides scientific arguments for taking decisive actions to improve air quality and reduce the global burden of disease associated with air pollution. PMID:24304307

  13. Terahertz study on porosity and mass fraction of active pharmaceutical ingredient of pharmaceutical tablets.

    PubMed

    Bawuah, Prince; Tan, Nicholas; Tweneboah, Samuel Nana A; Ervasti, Tuomas; Axel Zeitler, J; Ketolainen, Jarkko; Peiponen, Kai-Erik

    2016-08-01

    In this study, terahertz time-domain spectroscopic (THz-TDS) technique has been used to ascertain the change in the optical properties, as a function of changing porosity and mass fraction of active pharmaceutical ingredient (API), of training sets of pharmaceutical tablets. Four training sets of pharmaceutical tablets were compressed with microcrystalline cellulose (MCC) excipient and indomethacin API by varying either the porosity, height, and API mass fraction or all three tablet parameters. It was observed, as far as we know, for the first time, that the THz time-domain and frequency-domain effective refractive index, as well as, the frequency-domain effective absorption coefficient both show linear correlations with the porosity and API mass fraction for training sets of real pharmaceutical tablets. We suggest that, the observed linear correlations can be useful in basic research and quality inspection of pharmaceutical tablets. Additionally, we propose a novel optical strain parameter, based on THz measurement, which yields information on the conventional strain parameter of a tablet as well as on the change of fill fraction of solid material during compression of porous pharmaceutical tablets. We suggest that the THz measurement and proposed method of data analysis, in addition to providing an efficient tool for basic research of porous media, can serve as one of the novel quality by design (QbD) implementation techniques to predict critical quality attributes (CQA) such as porosity, API mass fraction and strain of flat-faced pharmaceutical tablets before production. PMID:27288937

  14. On the correlation of atmospheric aerosol components of mass size distributions in the larger region of a central European city

    NASA Astrophysics Data System (ADS)

    Berner, A.; Galambos, Z.; Ctyroky, P.; Frühauf, P.; Hitzenberger, R.; Gomišček, B.; Hauck, H.; Preining, O.; Puxbaum, H.

    Mass size distributions of atmospheric aerosols have been sampled in the region of Vienna, a typical city in central Europe, at an urban and a rural site. The aerosol was collected simultaneously by cascade impactors. Two experiments which had a duration of 4 weeks each, were performed in August 1999 and in January/February 2000. Daily sampling periods were from 8:00 to 20:00, and from 20:00 to 8:00. An evaluation of the mass size distributions is represented in this paper. Emphasis is on the relationships of different aerosol components in a local and a regional context. The main results are as follows. The main components of the atmospheric aerosol are a fine aerosol, the accumulation aerosol, and a coarse aerosol. Specific coarse modes with modal diameters of 4.7 μm average and geometric standard deviations of about 3 occur at the urban and at the rural site, some times surprisingly strong. The fine and the coarse modes are very likely related to motor-car traffic. Usually the PM 2.5 and PM 10 aerosols are regionally strongly correlated. Occasionally, this correlation is effectively disturbed by local and/or regional emissions. Time series of correlation coefficients reveal an episodic character of the atmospheric aerosol. Periods of strong inter-site correlations of PM 2.5 and PM 10 indicate the dominance and the co-variation of the accumulation aerosols or the dominance and the co-variation of the coarse modes.

  15. In situ observations of aerosol and chlorine monoxide after the 1991 eruption of Mount Pinatubo - Effect of reactions on sulfate aerosol

    NASA Technical Reports Server (NTRS)

    Wilson, J. C.; Jonsson, H. H.; Brock, C. A.; Toohey, D. W.; Avallone, L. M.; Baumgardner, D.; Dye, J. E.; Poole, L. R.; Woods, D. C.; Decoursey, R. J.

    1993-01-01

    Highly resolved aerosol size distributions measured from high-altitude aircraft can be used to describe the effect of the 1991 eruption of Mount Pinatubo on the stratospheric aerosol. In some air masses, aerosol mass mixing ratios increased by factors exceeding 100 and aerosol surface area concentrations increased by factors of 30 or more. Increases in aerosol surface area concentration were accompanied by increases in chlorine monoxide at mid-latitudes when confounding factors were controlled. This observation supports the assertion that reactions occurring on the aerosol can increase the fraction of stratospheric chlorine that occurs in ozone-destroying forms.

  16. Mapping and elemental fractionation of aerosols generated by laser-induced breakdown ablation.

    PubMed

    Chen, Yuheng; Bulatov, Valery; Singer, Liviu; Stricker, Josef; Schechter, Israel

    2005-12-01

    Laser-induced breakdown spectroscopy (LIBS) has been used to map the distribution of particulate matter inside the plume created by laser ablation of a brass target. The spatial density distribution of the different components of the plume was determined in an attempt to reveal the mechanism of fractionation in the process of the laser ablation. In this experiment two Nd:YAG pulsed lasers were used. The first beam was focused on the target to generate a plume after breakdown of the surface. The second laser was focused on the plume and generated the second breakdown. The composition of the region probed by the second beam was determined by analyzing the spectral emission from the second breakdown. By scanning the probe time and position, the temporal and spatial evolution of the laser ablative plume could be discovered. Spatial and temporal fractionation was observed in brass plume.

  17. Polar and non-polar organic aerosols from large-scale agricultural-waste burning emissions in Northern India: Implications to organic mass-to-organic carbon ratio.

    PubMed

    Rajput, Prashant; Sarin, M M

    2014-05-01

    This study focuses on characteristics of organic aerosols (polar and non-polar) and total organic mass-to-organic carbon ratio (OM/OC) from post-harvest agricultural-waste (paddy- and wheat-residue) burning emissions in Northern India. Aerosol samples from an upwind location (Patiala: 30.2°N, 76.3°E) in the Indo-Gangetic Plain were analyzed for non-polar and polar fractions of organic carbon (OC1 and OC2) and their respective mass (OM1 and OM2). On average, polar organic aerosols (OM2) contribute nearly 85% of the total organic mass (OM) from the paddy- and wheat-residue burning emissions. The water-soluble-OC (WSOC) to OC2 ratio, within the analytical uncertainty, is close to 1 from both paddy- and wheat-residue burning emissions. However, temporal variability and relatively low WSOC/OC2 ratio (Av: 0.67±0.06) is attributed to high moisture content and poor combustion efficiency during paddy-residue burning, indicating significant contribution (∼30%) of aromatic carbon to OC2. The OM/OC ratio for non-polar (OM1/OC1∼1.2) and polar organic aerosols (OM2/OC2∼2.2), hitherto unknown for open agricultural-waste burning emissions, is documented in this study. The total OM/OC ratio is nearly identical, 1.9±0.2 and 1.8±0.2, from paddy- and wheat-residue burning emissions.

  18. From Regional Cloud-Albedo to a Global Albedo Footprint - Studying Aerosol Effects on the Radiation Budget Using the Relation Between Albedo and Cloud Fraction

    NASA Astrophysics Data System (ADS)

    Bender, F.; Engström, A.; Karlsson, J.; Wood, R.; Charlson, R. J.

    2015-12-01

    Earth's albedo is the primary determinant of the amount of energy absorbed by the Earth-atmosphere system. The main factor controlling albedo is the amount of clouds present, but aerosols can affect and alter both clear-sky and cloudy-sky reflectance. How albedo depends on cloud fraction and how albedo varies at a given cloud fraction and a given cloud water content, reveals information about these aerosol effects on the radiation budget. Hence, the relation between total albedo and cloud fraction can be used for illustration and quantification of aerosol effects, and as a diagnostic tool, to test model performance. Here, we show examples of the utilisation of this relation focusing on satellite observations from CERES and MODIS on Aqua, as well as from Calipso and CloudSat, and performing comparisons with climate models on the way: In low-cloud regions in the subtropics, we find that climate models well represent a near-constant regional cloud albedo, and this representation has improved from CMIP3 to CMIP5. CMIP5 models indicate more reflective clouds in present-day climate than pre-industrial, as a result of increased aerosol burdens. On monthly mean time scale, models are found to over-estimate the regional cloud-brightening due to aerosols. On the global scale we find an increasing cloud albedo with increasing cloud fraction - a relation that is very well defined in observations, and less so in CMIP5 models. Cloud brightening from pre-industrial to present day is also seen on global scale. Further, controlling for both cloud fraction and cloud water content we can trace small variations in albedo, or perturbations of solar reflectivity, that create a near-global coherent geographical pattern that is consistent with aerosol impacts on climate, with albedo enhancement in regions dominant of known aerosol sources and suppression of albedo in regions associated with high rates of aerosol removal (deduced using CloudSat precipitation estimates). This mapping can be

  19. Extractive Electrospray Ionization Mass Spectrometry of Heterogeneous Particles: Implications for Applications to Complex Atmospheric Aerosol

    NASA Astrophysics Data System (ADS)

    Longin, T.; Waring-Kidd, C.; Wingen, L. M.; Lyster, K.; Anderson, C.; Kumbhani, S.; Finlayson-Pitts, B. J.

    2015-12-01

    Extractive electrospray ionization mass spectrometry (EESI-MS) is a direct, real time technique for obtaining mass spectra of gases, liquid droplets, solid particles, and aerosols with little sample processing. EESI-MS involves the interaction of charged electrospray droplets with a separate spray containing the analyte of interest, but the exact mechanism by which the solvent droplets extract analyte from the sample is unclear. Possible mechanisms include complete coalescence of the sample particle with the solvent droplet in which all of the analyte is incorporated into the solvent or a more temporary interaction such that only some of the analyte is transferred to the solvent. Previous studies of the mechanism of EESI-MS on homogeneous particles indicate that both mechanisms are possible. We studied the behavior of EESI-MS toward heterogeneous particles created by coating NaCl particles with various thicknesses of organic diacids. Our results indicate that the signal strength depends on the solubility of the organic acid in the electrospray solvent, in agreement with previous studies, and also that the outer 10-15 nm of the particles are most susceptible to extraction into the electrospray droplets. Our results combined with those of previous studies suggest that the mass spectra obtained with EESI will not necessarily reflect the overall particle composition, especially for particles that are spatially inhomogeneous, and hence caution in interpretation of the data is advised for application to complex atmospheric aerosol.

  20. High-Resolution Desorption Electrospray Ionization Mass Spectrometry for Chemical Characterization of Organic Aerosols

    SciTech Connect

    Laskin, Julia; Laskin, Alexander; Roach, Patrick J.; Slysz, Gordon W.; Anderson, Gordon A.; Nizkorodov, Serguei; Bones, David L.; Nguyen, Lucas

    2010-03-01

    Characterization of the chemical composition and chemical transformations of secondary organic aerosol (SOA) is both a major challenge and the area of greatest uncertainty in current aerosol research. This study presents the first application of desorption electrospray ionization combined with high-resolution mass spectrometry (DESI-MS) for detailed chemical characterization and studies of chemical aging of OA collected on Teflon substrates. DESI-MS offers unique advantages both for detailed characterization of chemically labile components in OA that cannot be detected using more traditional electrospray ionization mass spectrometry (ESI-MS) and for studying chemical aging of OA. DESI-MS enables rapid characterization of OA samples collected on substrates by eliminating the sample preparation stage. In addition, it enables detection and structural characterization of chemically labile molecules in OA samples by minimizing the residence time of analyte in the solvent. SOA produced by the ozonolysis of limonene (LSOA) was allowed to react with gaseous ammonia. Chemical aging resulted in measurable changes in the optical properties of LSOA observed using UV- visible spectroscopy. DESI-MS combined with tandem mass spectrometry experiments (MS/MS) enabled identification of species in aged LSOA responsible for absorption of the visible light. Detailed analysis of the experimental data allowed us to identify chemical changes induced by reactions of LSOA constituents with ammonia and distinguish between different mechanisms of chemical aging.

  1. Molecular Chemistry of Organic Aerosols Through the Application of High Resolution Mass Spectrometry

    SciTech Connect

    Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2011-01-05

    Understanding of molecular composition and fundamental chemical transformations of organic aerosols (OA) during their formation and aging is both a major challenge and the area of greatest uncertainty in atmospheric research. Particularly little is known about fundamental relationship between the chemical composition and physicochemical properties of OA, their atmospheric history, evolution, and impact on the environment. Ambient soft-ionization methods combined with high-resolution mass spectrometry (HR-MS) analysis provide detailed information on the molecular content of OA that is pivotal for improved understanding of their complex composition, multi-phase aging chemistry, direct (light absorption and scattering) and indirect (aerosol-cloud interactions) effects on atmospheric radiation and climate, and health effects. The HR-MS methods can detect thousands of individual OA constituents at once, provide their elemental formulae from accurate mass measurements, and provide structural information based on tandem mass spectrometry. Integration with additional analytical tools, such as chromatography and UV/Vis absorption spectroscopy, makes it possible to further separate OA compounds by their polarity and ability to absorb solar radiation. The goal of this perspective is to describe modern HR-MS methods, review recent applications to field and laboratory studies of OA, and explain how the information obtained from HR-MS methods can be translated into improved understanding of OA chemistry.

  2. Iron-Isotopic Fractionation Studies Using Multiple Collector Inductively Coupled Plasma Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Anbar, A. D.; Zhang, C.; Barling, J.; Roe, J. E.; Nealson, K. H.

    1999-01-01

    The importance of Fe biogeochemistry has stimulated interest in Fe isotope fractionation. Recent studies using thermal ionization mass spectrometry (TIMS) and a "double spike" demonstrate the existence of biogenic Fe isotope effects. Here, we assess the utility of multiple-collector inductively-coupled plasma mass spectrometry(MC-ICP-MS) with a desolvating sample introduction system for Fe isotope studies, and present data on Fe biominerals produced by a thermophilic bacterium. Additional information is contained in the original extended abstract.

  3. An empirical method for the determination of the complex refractive index of size-fractionated atmospheric aerosols for radiative transfer calculations.

    SciTech Connect

    Marley, N. A.; Gaffney, J. S.; Baird, J. C.; Drayton, P. J.; Frederick, J. E.; Environmental Research; Univ. of Chicago

    2001-06-01

    To adequately assess the effects of atmospheric aerosols on climate, their optical constants (scattering and absorption coefficients) must be known. The absorption and scattering coefficients of the aerosols are derived from the real and imaginary parts of the complex refractive index and are dependent on their size and chemical composition. Because aerosol properties vary significantly with location, it is difficult to assign values for the absorption and scattering of solar radiation by aerosols in models of global climate change. This study reports a new method of collecting size-fractionated atmospheric aerosol samples for the purpose of directly measuring their transmission and reflectance spectra followed by the determination of the complex refractive index across the entire atmospherically relevant spectral range. The samples were collected with a modified Sierra high-volume cascade impactor with the usual filter collection surfaces replaced with Teflon sheets machined to hold quartz (ultraviolet [UV]/visible transparent) and/or silver chloride (infrared transparent) sample collection plates. Reflectance and transmission spectra can be obtained on the aerosol samples directly as a function of wavelength, from 280 nm to 2.5 m, with an integrating sphere coupled to an UV/visible or a Fourier transform infrared (FTIR) spectrophotometer. The effective real and imaginary components of the refractive index of the bulk sample material can then be approximated, as a function of wavelength, from the sample spectra. Preliminary results are presented for carbon soot samples generated in the laboratory and for standard diesel soot samples in the UV/visible spectral range. These are compared to results obtained for size-fractionated atmospheric aerosol samples collected near Pasco, WA, West Mesa, AZ, and Argonne, IL.

  4. Extensive aerosol optical properties and aerosol mass related measurements during TRAMP/TexAQS 2006 - Implications for PM compliance and planning

    NASA Astrophysics Data System (ADS)

    Wright, Monica E.; Atkinson, Dean B.; Ziemba, Luke; Griffin, Robert; Hiranuma, Naruki; Brooks, Sarah; Lefer, Barry; Flynn, James; Perna, Ryan; Rappenglück, Bernhard; Luke, Winston; Kelley, Paul

    2010-10-01

    Extensive aerosol optical properties, particle size distributions, and Aerodyne quadrupole aerosol mass spectrometer measurements collected during TRAMP/TexAQS 2006 were examined in light of collocated meteorological and chemical measurements. Much of the evident variability in the observed aerosol-related air quality is due to changing synoptic meteorological situations that direct emissions from various sources to the TRAMP site near the center of the Houston-Galveston-Brazoria (HGB) metropolitan area. In this study, five distinct long-term periods have been identified. During each of these periods, observed aerosol properties have implications that are of interest to environmental quality management agencies. During three of the periods, long range transport (LRT), both intra-continental and intercontinental, appears to have played an important role in producing the observed aerosol. During late August 2006, southerly winds brought super-micron Saharan dust and sea salt to the HGB area, adding mass to fine particulate matter (PM 2.5) measurements, but apparently not affecting secondary particle growth or gas-phase air pollution. A second type of LRT was associated with northerly winds in early September 2006 and with increased ozone and sub-micron particulate matter in the HGB area. Later in the study, LRT of emissions from wildfires appeared to increase the abundance of absorbing aerosols (and carbon monoxide and other chemical tracers) in the HGB area. However, the greatest impacts on Houston PM 2.5 air quality are caused by periods with low-wind-speed sea breeze circulation or winds that directly transport pollutants from major industrial areas, i.e., the Houston Ship Channel, into the city center.

  5. Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates

    PubMed Central

    Miller, Martin F.; Franchi, Ian A.; Thiemens, Mark H.; Jackson, Teresa L.; Brack, André; Kurat, Gero; Pillinger, Colin T.

    2002-01-01

    Nearly all chemical processes fractionate 17O and 18O in a mass-dependent way relative to 16O, a major exception being the formation of ozone from diatomic oxygen in the presence of UV radiation or electrical discharge. Investigation of oxygen three-isotope behavior during thermal decomposition of naturally occurring carbonates of calcium and magnesium in vacuo has revealed that, surprisingly, anomalous isotopic compositions are also generated during this process. High-precision measurements of the attendant three-isotope fractionation line, and consequently the magnitude of the isotopic anomaly (Δ17O), demonstrate that the slope of the line is independent of the nature of the carbonate but is controlled by empirical factors relating to the decomposition procedure. For a slope identical to that describing terrestrial silicates and waters (0.5247 ± 0.0007 at the 95% confidence level), solid oxides formed during carbonate pyrolysis fit a parallel line offset by −0.241 ± 0.042‰. The corresponding CO2 is characterized by a positive offset of half this magnitude, confirming the mass-independent nature of the fractionation. Slow, protracted thermolysis produces a fractionation line of shallower slope (0.5198 ± 0.0007). These findings of a 17O anomaly being generated from a solid, and solely by thermal means, provide a further challenge to current understanding of the nature of mass-independent isotopic fractionation. PMID:12167677

  6. Sources and composition of submicron organic mass in marine aerosol particles

    SciTech Connect

    Frossard, Amanda A.; Russell, Lynn M.; Burrows, Susannah M.; Elliott, Scott M.; Bates, Timothy S.; Quinn, Patricia K.

    2014-11-27

    Recent studies have proposed a variety of interpretations of the sources and composition of atmospheric marine aerosol particles (aMA) based on a range of physical and chemical measurements collected during open-ocean research cruises. To investigate the processes that affect marine organic particles, this study uses the characteristic functional group composition (from Fourier transform infrared (FTIR) spectroscopy) of aMAP from five ocean regions to show that: (i) The organic functional group composition of aMAP that can be identified as atmospheric primary marine (ocean-derived) aerosol (aPMA) is 65±12% hydroxyl, 21±9% alkane, 6±6% amine, and 7±8% carboxylic acid functional groups. Contributions from photochemical reactions add carboxylic acid groups (15%-25%), shipping effluent in seawater and ship emissions add additional alkane groups (up to 70%), and coastal emissions mix in alkane and carboxylic acid groups from coastal pollution sources. (ii) The organic composition of aPMA is nearly identical to model generated primary marine aerosol particles (gPMA) from bubbled seawater (55% hydroxyl, 32% alkane, and 13% amine functional groups), indicating that its overall functional group composition is the direct consequence of the organic constituents of the seawater source. (iii) While the seawater organic functional group composition was nearly invariant across all three ocean regions studied, the gPMA alkane group fraction increased with chlorophyll-a concentrations (r = 0.79). gPMA from productive seawater had a larger fraction of alkane functional groups (35%) compared to gPMA from non-productive seawater (16%), likely due to the presence of surfactants in productive seawater that stabilize the bubble film and lead to preferential drainage of the more soluble (lower alkane group fraction) organic components. gPMA has a hydroxyl group absorption peak location characteristic of monosaccharides and disaccharides, where the seawater OM hydroxyl group peak

  7. Sources and composition of submicron organic mass in marine aerosol particles

    DOE PAGES

    Frossard, Amanda A.; Russell, Lynn M.; Burrows, Susannah M.; Elliott, Scott M.; Bates, Timothy S.; Quinn, Patricia K.

    2014-11-27

    Recent studies have proposed a variety of interpretations of the sources and composition of atmospheric marine aerosol particles (aMA) based on a range of physical and chemical measurements collected during open-ocean research cruises. To investigate the processes that affect marine organic particles, this study uses the characteristic functional group composition (from Fourier transform infrared (FTIR) spectroscopy) of aMAP from five ocean regions to show that: (i) The organic functional group composition of aMAP that can be identified as atmospheric primary marine (ocean-derived) aerosol (aPMA) is 65±12% hydroxyl, 21±9% alkane, 6±6% amine, and 7±8% carboxylic acid functional groups. Contributions from photochemicalmore » reactions add carboxylic acid groups (15%-25%), shipping effluent in seawater and ship emissions add additional alkane groups (up to 70%), and coastal emissions mix in alkane and carboxylic acid groups from coastal pollution sources. (ii) The organic composition of aPMA is nearly identical to model generated primary marine aerosol particles (gPMA) from bubbled seawater (55% hydroxyl, 32% alkane, and 13% amine functional groups), indicating that its overall functional group composition is the direct consequence of the organic constituents of the seawater source. (iii) While the seawater organic functional group composition was nearly invariant across all three ocean regions studied, the gPMA alkane group fraction increased with chlorophyll-a concentrations (r = 0.79). gPMA from productive seawater had a larger fraction of alkane functional groups (35%) compared to gPMA from non-productive seawater (16%), likely due to the presence of surfactants in productive seawater that stabilize the bubble film and lead to preferential drainage of the more soluble (lower alkane group fraction) organic components. gPMA has a hydroxyl group absorption peak location characteristic of monosaccharides and disaccharides, where the seawater OM hydroxyl group

  8. Molecular composition of fresh and aged secondary organic aerosol from a mixture of biogenic volatile compounds: a high-resolution mass spectrometry study

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Doussin, J.-F.; Giorio, C.; Mahon, B.; Wilson, E. M.; Maurin, N.; Pangui, E.; Venables, D. S.; Wenger, J. C.; Kalberer, M.

    2015-05-01

    Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidized molecules. Aerosol processing or further oxidation (aging) of organic aerosol has been suggested to be responsible for their formation through heterogeneous reaction with oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several aging processes on the molecular composition of secondary organic aerosols (SOA) using direct infusion and liquid chromatography high-resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC): α-pinene, β-pinene, Δ3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated aging was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC) and elemental O / C ratios of the SOA components. None of the aging processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using α-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH-initiated oxidation of α-pinene had a significantly higher overall OSC and O / C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidized species in ambient biogenic SOA.

  9. 40 CFR Table 5 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Wood Building Products Pt. 63, Subpt. QQQQ, Table 5 Table 5 to Subpart QQQQ of Part 63—Default Organic.... Solvent/solvent blend CAS. No. Average organic HAP mass fraction Typical organic HAP, percent by mass...

  10. 40 CFR Table 6 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Wood Building Products Pt. 63, Subpt. QQQQ, Table 6 Table 6 to Subpart QQQQ of Part 63—Default Organic... type Average organic HAP mass fraction Typical organic HAP, percent by mass Aliphatic b 0.03 1%...

  11. 40 CFR Table 4 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Large Appliances Pt. 63, Subpt. NNNN, Table 4 Table 4 to Subpart NNNN of Part 63—Default Organic HAP... type Average organic HAP mass fraction Typical organic HAP, percent by mass Aliphatic b 0.03 1%...

  12. 40 CFR Table 4 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Large Appliances Pt. 63, Subpt. NNNN, Table 4 Table 4 to Subpart NNNN of Part 63—Default Organic HAP... type Average organic HAP mass fraction Typical organic HAP, percent by mass Aliphatic b 0.03 1%...

  13. 40 CFR Table 3 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Default Organic HAP Mass Fraction for... Large Appliances Pt. 63, Subpt. NNNN, Table 3 Table 3 to Subpart NNNN of Part 63—Default Organic HAP.../solvent blend CAS. No. Average organic HAP mass fraction Typical organic HAP, percent by mass 1....

  14. 40 CFR Table 3 to Subpart Nnnn of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Mass Fraction for... Large Appliances Pt. 63, Subpt. NNNN, Table 3 Table 3 to Subpart NNNN of Part 63—Default Organic HAP.../solvent blend CAS. No. Average organic HAP mass fraction Typical organic HAP, percent by mass 1....

  15. Fullerene Soot in Eastern China Air: Results from Soot Particle-Aerosol Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Wang, J.; Ge, X.; Chen, M.; Zhang, Q.; Yu, H.; Sun, Y.; Worsnop, D. R.; Collier, S.

    2015-12-01

    In this work, we present for the first time, the observation and quantification of fullerenes in ambient airborne particulate using an Aerodyne Soot Particle - Aerosol Mass Spectrometer (SP-AMS) deployed during 2015 winter in suburban Nanjing, a megacity in eastern China. The laser desorption and electron impact ionization techniques employed by the SP-AMS allow us to differentiate various fullerenes from other aerosol components. Mass spectrum of the identified fullerene soot is consisted by a series of high molecular weight carbon clusters (up to m/z of 2000 in this study), almost identical to the spectral features of commercially available fullerene soot, both with C70 and C60 clusters as the first and second most abundant species. This type of soot was observed throughout the entire study period, with an average mass loading of 0.18 μg/m3, accounting for 6.4% of the black carbon mass, 1.2% of the total organic mass. Temporal variation and diurnal pattern of fullerene soot are overall similar to those of black carbon, but are clearly different in some periods. Combining the positive matrix factorization, back-trajectory and analyses of the meteorological parameters, we identified the petrochemical industrial plants situating upwind from the sampling site, as the major source of fullerene soot. In this regard, our findings imply the ubiquitous presence of fullerene soot in ambient air of industry-influenced area, especially the oil and gas production regions. This study also offers new insights into the characterization of fullerenes from other environmental samples via the advanced SP-AMS technique.

  16. Aerosol properties, source identification, and cloud processing in orographic clouds measured by single particle mass spectrometry on a Central European mountain site during HCCT-2010

    NASA Astrophysics Data System (ADS)

    Roth, A.; Schneider, J.; Klimach, T.; Mertes, S.; van Pinxteren, D.; Herrmann, H.; Borrmann, S.

    2015-09-01

    Cloud residues and out-of-cloud aerosol particles with diameters between 150 and 900 nm have been analysed by on-line single particle aerosol mass spectrometry during the six-week study HCCT-2010 in September/October 2010. The measurement location was the mountain Schmücke (937 m a.s.l.) in Central Germany. More than 170 000 bipolar mass spectra from out-of-cloud aerosol particles and more than 14 000 bipolar mass spectra from cloud residual particles were obtained and were classified using a fuzzy c-means clustering algorithm. Analysis of the uncertainty of the sorting algorithm was conducted on a subset of the data by comparing the clustering output with particle-by-particle inspection and classification by the operator. This analysis yielded a false classification probability between 13 and 48 %. Additionally, particle types were identified by specific marker ions. The results from the ambient aerosol analysis show that 63 % of the analysed particles belong to clusters indicating a diurnal variation, suggesting that local or regional sources dominate the aerosol, especially for particles containing soot and biomass burning particles. In the cloud residues the relative percentage of large soot-containing particles and particles containing amines was found to be increased compared to the out-of-cloud aerosol, while in general organic particles were less abundant in the cloud residues. In the case of amines this can be explained by the high solubility of the amines, while the large soot-containing particles were found to be internally mixed with inorganics, which explains their activation as cloud condensation nuclei. Furthermore, the results show that during cloud processing, both sulphate and nitrate are added to the residual particles, thereby changing the mixing state and increasing the fraction of particles with nitrate and/or sulphate. This is expected to lead to higher hygroscopicity after cloud evaporation, and therefore to an increase of the particles

  17. Aerosol properties, source identification, and cloud processing in orographic clouds measured by single particle mass spectrometry on a central European mountain site during HCCT-2010

    NASA Astrophysics Data System (ADS)

    Roth, A.; Schneider, J.; Klimach, T.; Mertes, S.; van Pinxteren, D.; Herrmann, H.; Borrmann, S.

    2016-01-01

    Cloud residues and out-of-cloud aerosol particles with diameters between 150 and 900 nm were analysed by online single particle aerosol mass spectrometry during the 6-week study Hill Cap Cloud Thuringia (HCCT)-2010 in September-October 2010. The measurement location was the mountain Schmücke (937 m a.s.l.) in central Germany. More than 160 000 bipolar mass spectra from out-of-cloud aerosol particles and more than 13 000 bipolar mass spectra from cloud residual particles were obtained and were classified using a fuzzy c-means clustering algorithm. Analysis of the uncertainty of the sorting algorithm was conducted on a subset of the data by comparing the clustering output with particle-by-particle inspection and classification by the operator. This analysis yielded a false classification probability between 13 and 48 %. Additionally, particle types were identified by specific marker ions. The results from the ambient aerosol analysis show that 63 % of the analysed particles belong to clusters having a diurnal variation, suggesting that local or regional sources dominate the aerosol, especially for particles containing soot and biomass burning particles. In the cloud residues, the relative percentage of large soot-containing particles and particles containing amines was found to be increased compared to the out-of-cloud aerosol, while, in general, organic particles were less abundant in the cloud residues. In the case of amines, this can be explained by the high solubility of the amines, while the large soot-containing particles were found to be internally mixed with inorganics, which explains their activation as cloud condensation nuclei. Furthermore, the results show that during cloud processing, both sulfate and nitrate are added to the residual particles, thereby changing the mixing state and increasing the fraction of particles with nitrate and/or sulfate. This is expected to lead to higher hygroscopicity after cloud evaporation, and therefore to an increase of

  18. Comment on 'A non-mass-dependent isotopic fractionation effect' by F. Robert, J. Halbout and J. Baudon

    NASA Technical Reports Server (NTRS)

    Sund, Mark T.

    1990-01-01

    The fractionation model of Robert et al. (1988) treats the gas-phase isotopic exchange reaction between kinetically excited atoms aX and diatomic MbX yielding bX and MaX and finds an abundance-dependent fractionation superimposed on the usual mass dependent fractionation. This paper shows that the treatment of Robert et al. is in error and presents a more straightforward treatment of the same system. This model shows only mass-dependent fractionation.

  19. Iron and nickel isotopic mass fractionation in deep-sea spherules

    NASA Technical Reports Server (NTRS)

    Davis, Andrew M.; Brownlee, Donald E.

    1993-01-01

    Magnetite-wuestite spherules collected from deep-sea sediments are thought to have originally been Fe-Ni metal particles at the top of the atmosphere that were oxidized and melted during entry into the earth's atmosphere. Some likely sources for the metal particles are Fe-Ni interplanetary dust particles (IDP's) and metal or sulfide from stony IDP's that separated after melting. Davis et al. reported that four of these spherules are enriched in the heavy isotopes of iron, with enrichments of 8-23%/amu. We have developed a technique for analysis of both iron and nickel isotopes on the same ion microprobe spot and have applied this technique to a number of deep-sea spherules in order to better understand the processes leading to isotopic mass fractionation. Eight spherules show iron and nickel isotopic mass fractionation, with iron and nickel enriched in the heavy isotopes by 10-19%/amu and 4-32%/amu, respectively. If the mass fractionations are due to Rayleigh fractionation during evaporation, these spherules lost 76-94% of their original mass. We have analyzed the four magnetite-wuestite spherules for which iron isotopic data were reported by Davis et al. as well as four new spherules.

  20. The X-ray/SZ view of the virial region. II. Gas mass fraction

    NASA Astrophysics Data System (ADS)

    Eckert, D.; Ettori, S.; Molendi, S.; Vazza, F.; Paltani, S.

    2013-03-01

    Aims: Several recent studies used the hot gas fraction of galaxy clusters as a standard ruler to constrain dark energy, which provides competitive results compared to other techniques. This method, however, relies on the assumption that the baryon fraction in clusters agrees with the cosmic value Ωb/Ωm, and does not differ from one system to another. We test this hypothesis by measuring the gas mass fraction over the entire cluster volume in a sample of local clusters. Methods: Combining the Sunyaev-Zel'dovich thermal pressure from Planck and the X-ray gas density from ROSAT, we measured for the first time the average gas fraction (fgas) out to the virial radius and beyond in a large sample of clusters. We also obtained azimuthally-averaged measurements of the gas fraction for 18 individual systems, which we used to compute the scatter of fgas around the mean value at different radii and its dependence on the cluster's temperature. Results: The gas mass fraction increases with radius and reaches the cosmic baryon fraction close to R200. At R200, we measure fgas,200 = 0.176 ± 0.009 (0.166 ± 0.012 for the subsample of 18 clusters in common between Planck and ROSAT). We find significant differences between the baryon fraction of relaxed, cool-core (CC) systems and unrelaxed, non-cool core (NCC) clusters in the outer regions. On average, the gas fraction in NCC clusters slightly exceeds the cosmic baryon fraction, while in CC systems the gas fraction converges to the expected value when accounting for the stellar content, without any evidence for variations from one system to another. Conclusions: We find that fgas estimates in NCC systems slightly disagree with the cosmic value approaching R200. This result could be explained either by a violation of the assumption of hydrostatic equilibrium or by an inhomogeneous distribution of the gas mass. Conversely, CC clusters are found to provide reliable constraints on fgas at overdensities Δ > 200, which makes them

  1. Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples.

    PubMed

    El-Zanan, Hazem S; Lowenthal, Douglas H; Zielinska, Barbara; Chow, Judith C; Kumar, Naresh

    2005-07-01

    The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.

  2. Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples.

    PubMed

    El-Zanan, Hazem S; Lowenthal, Douglas H; Zielinska, Barbara; Chow, Judith C; Kumar, Naresh

    2005-07-01

    The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low. PMID:15950041

  3. Mass fractionation of noble gases in diffusion-limited hydrodynamic hydrogen escape

    NASA Technical Reports Server (NTRS)

    Zahnle, Kevin; Pollack, James B.; Kasting, James F.

    1990-01-01

    The theory of mass fractionation by hydrogen is presently extended to atmospheres in which hydrogen is not the major constituent. This theoretical framework is applied to three different cases. In the first, it is shown that the fractionation of terrestrial atmospheric neon with respect to mantle neon is explainable as a consequence of diffusion-limited hydrogen escape from a steam atmosphere toward the end of the accretion process. In the second, the anomalously high Ar-38/Ar-36 ratio of Mars is shown to be due to hydrodynamic fractionation by a vigorously escaping and very pure hydrogen wind. In the last case, it is speculated that the currently high Martian D/H ratio emerged during the hydrodynamic escape phase which fractionated Ar.

  4. Constraining Aerosol Optical Models Using Ground-Based, Collocated Particle Size and Mass Measurements in Variable Air Mass Regimes During the 7-SEAS/Dongsha Experiment

    NASA Technical Reports Server (NTRS)

    Bell, Shaun W.; Hansell, Richard A.; Chow, Judith C.; Tsay, Si-Chee; Wang, Sheng-Hsiang; Ji, Qiang; Li, Can; Watson, John G.; Khlystov, Andrey

    2012-01-01

    During the spring of 2010, NASA Goddard's COMMIT ground-based mobile laboratory was stationed on Dongsha Island off the southwest coast of Taiwan, in preparation for the upcoming 2012 7-SEAS field campaign. The measurement period offered a unique opportunity for conducting detailed investigations of the optical properties of aerosols associated with different air mass regimes including background maritime and those contaminated by anthropogenic air pollution and mineral dust. What appears to be the first time for this region, a shortwave optical closure experiment for both scattering and absorption was attempted over a 12-day period during which aerosols exhibited the most change. Constraints to the optical model included combined SMPS and APS number concentration data for a continuum of fine and coarse-mode particle sizes up to PM2.5. We also take advantage of an IMPROVE chemical sampler to help constrain aerosol composition and mass partitioning of key elemental species including sea-salt, particulate organic matter, soil, non sea-salt sulphate, nitrate, and elemental carbon. Our results demonstrate that the observed aerosol scattering and absorption for these diverse air masses are reasonably captured by the model, where peak aerosol events and transitions between key aerosols types are evident. Signatures of heavy polluted aerosol composed mostly of ammonium and non sea-salt sulphate mixed with some dust with transitions to background sea-salt conditions are apparent in the absorption data, which is particularly reassuring owing to the large variability in the imaginary component of the refractive indices. Extinctive features at significantly smaller time scales than the one-day sample period of IMPROVE are more difficult to reproduce, as this requires further knowledge concerning the source apportionment of major chemical components in the model. Consistency between the measured and modeled optical parameters serves as an important link for advancing remote

  5. Mass size distributions of water-soluble inorganic and organic ions in size-segregated aerosols over metropolitan Newark in the US east coast

    NASA Astrophysics Data System (ADS)

    Zhao, Yunliang; Gao, Yuan

    2008-06-01

    To characterize the mass size distributions of water-soluble inorganic and organic ions associated with urban particulate matter, a total of 15 sets of size-segregated aerosol samples were collected by a 10-stage Micro-Orifice Uniform Deposit Impactor (MOUDI) in the urban area of Newark in New Jersey from July to December 2006. The mass concentrations of PM1.8 accounted for ∼68% of the mass concentrations of PM10. The mass concentrations of the total water-soluble ions in PM1.8 accounted for 31-81% of the mass concentrations of PM1.8. Sulfate was the dominant ion in fine particles, accounting for 31% of the PM1.8 mass with its dominant mode at 0.32-0.56 μm throughout all the samples. Nitrate size distributions were bi-modal, peaking at 0.32-0.56 and 3.2-5.6 μm, and the shift of the nitrate dominant fraction between fine and coarse modes was affected by temperature. The ratios of nitrate to PM1.8 varied significantly, 0.5-27%. The C2-C4 dicarboxylic acids accounted for 1.9±0.9% of PM1.8 mass, with oxalate being the dominant ion. The size distributions of oxalate exhibited two to four modes with the dominant one at 0.32-0.56 μm. Chloride existed in both coarse and fine modes, suggesting the influence of sea-salt aerosol and anthropogenic emissions. A crucial formation mechanism for the mass size distributions of these ions observed at this location is likely to be a combination of the gas-to-particle conversion and in-cloud/fog processing.

  6. Aerosol composition and properties variation at the ground and over the column under different air masses advection in South Italy.

    PubMed

    Pavese, G; Lettino, A; Calvello, M; Esposito, F; Fiore, S

    2016-04-01

    Aerosol composition and properties variation under the advection of different air masses were investigated, as case studies, by contemporary measurements over the atmospheric column and at the ground in a semi-rural site in South Italy. The absence of local strong sources in this area allowed to characterize background aerosol and to compare particle mixing effects under various atmospheric circulation conditions. Aerosol optical depth (AOD) and Ǻngström parameters from radiometric measurements allowed the detection and identification of polluted, dust, and volcanic atmospheric conditions. AODs were the input for a suitable model to evaluate the columnar aerosol composition, according to six main atmospheric components (water-soluble, soot, sea salt accumulation, sea salt coarse, mineral dus,t and biological). Scanning electron microscope (SEM) analysis of particulate sampled with a 13-stage impactor at the ground showed not only fingerprints typical of the different air masses but also the effects of transport and aging on atmospheric particles, suggesting processes that changed their chemical and optical properties. Background columnar aerosol was characterized by 72% of water-soluble and soot, in agreement with ground-based findings that highlighted 60% of contribution from anthropogenic carbonate particles and soot. In general, a good agreement between ground-based and columnar results was observed. Under the advection of trans-boundary air masses, water-soluble and soot were always present in columnar aerosol, whereas, in variable percentages, sea salt and mineral particles characterized both dust and volcanic conditions. At the ground, sulfates characterized the amorphous matrix produced in finer stages by the evaporation of solutions of organic and inorganic aerosols. Sulfates were also one of the key players involved in heterogeneous chemical reactions, producing complex secondary aerosol, as such clay-sulfate internally mixed particle externally mixed

  7. Performance of an improved monodisperse aerosol generation interface for liquid chromatography/mass spectrometry

    SciTech Connect

    Winkler, P.C.; Perkins, D.D.; Williams, W.K.; Browner, R.F.

    1988-03-01

    An improved monodisperse aerosol generation interface for liquid chromatography/mass spectrometry interfacing (MAG-IC-LC/MS) is described. The interface has an aerodynamically superior momentum separator, which results in decreased analyte loss in passing through the interface. The interface is shown to perform well with a quadrupole mass spectrometer, in addition to earlier studies with a magnetic sector instrument. A new method of forming aerosol has been developed, which reduces the dead volume significantly over earlier designs. The performance of the interface has been evaluated by studying its capabilities for (1) generating electron impact spectra of searchable quality for selected compounds of interest, (2) operating with typical liquid chromatographic separation conditions, including reverse phase and gradient elution, and (3) providing low detection limits for both full scan and selective ion monitoring detection of a range of compounds. Studies include identification of the components of a mixture of cis and trans isomers of the thermally labile compound retinol (vitamin A) acetate. Full scan (m/z 80-350) electron impact spectra were readily obtained with 50-ng injection on-column. Detection limits for this compound were 10 ng full scan and 1 ng with selected ion monitoring. Identification of a free (nonderivatized) fatty acid mixture was also readily obtained, using a reversed-phase separation in gradient mode.

  8. Impact of maritime air mass trajectories on the Western European coast urban aerosol.

    PubMed

    Almeida, S M; Silva, A I; Freitas, M C; Dzung, H M; Caseiro, A; Pio, C A

    2013-01-01

    Lisbon is the largest urban area in the Western European coast. Due to this geographical position the Atlantic Ocean serves as an important source of particles and plays an important role in many atmospheric processes. The main objectives of this study were to (1) perform a chemical characterization of particulate matter (PM2.5) sampled in Lisbon, (2) identify the main sources of particles, (3) determine PM contribution to this urban area, and (4) assess the impact of maritime air mass trajectories on concentration and composition of respirable PM sampled in Lisbon. During 2007, PM2.5 was collected on a daily basis in the center of Lisbon with a Partisol sampler. The exposed Teflon filters were measured by gravimetry and cut into two parts: one for analysis by instrumental neutron activation analysis (INAA) and the other by ion chromatography (IC). Principal component analysis (PCA) and multilinear regression analysis (MLRA) were used to identify possible sources of PM2.5 and determine mass contribution. Five main groups of sources were identified: secondary aerosols, traffic, calcium, soil, and sea. Four-day backtracking trajectories ending in Lisbon at the starting sampling time were calculated using the HYSPLIT model. Results showed that maritime transport scenarios were frequent. These episodes were characterized by a significant decrease of anthropogenic aerosol concentrations and exerted a significant role on air quality in this urban area.

  9. DDA Computations of Porous Aggregates with Forsterite Crystals: Effects of Crystal Shape and Crystal Mass Fraction

    NASA Technical Reports Server (NTRS)

    Wooden, Diane H.; Lindsay, Sean S.; Harker, David; Woodward, Charles; Kelley, Michael S.; Kolokolova, Ludmilla

    2015-01-01

    Porous aggregate grains are commonly found in cometary dust samples and are needed to model cometary IR spectral energy distributions (SEDs). Models for thermal emissions from comets require two forms of silicates: amorphous and crystalline. The dominant crystal resonances observed in comet SEDs are from Forsterite (Mg2SiO4). The mass fractions that are crystalline span a large range from 0.0 < or = fcrystal < or = 0.74. Radial transport models that predict the enrichment of the outer disk (>25 AU at 1E6 yr) by inner disk materials (crystals) are challenged to yield the highend-range of cometary crystal mass fractions. However, in current thermal models, Forsterite crystals are not incorporated into larger aggregate grains but instead only are considered as discrete crystals. A complicating factor is that Forsterite crystals with rectangular shapes better fit the observed spectral resonances in wavelength (11.0-11.15 microns, 16, 19, 23.5, 27, and 33 microns), feature asymmetry and relative height (Lindley et al. 2013) than spherically or elliptically shaped crystals. We present DDA-DDSCAT computations of IR absorptivities (Qabs) of 3 micron-radii porous aggregates with 0.13 < or = fcrystal < or = 0.35 and with polyhedral-shaped Forsterite crystals. We can produce crystal resonances with similar appearance to the observed resonances of comet Hale- Bopp. Also, a lower mass fraction of crystals in aggregates can produce the same spectral contrast as a higher mass fraction of discrete crystals; the 11micron and 23 micron crystalline resonances appear amplified when crystals are incorporated into aggregates composed otherwise of spherically shaped amorphous Fe-Mg olivines and pyroxenes. We show that the optical properties of a porous aggregate is not linear combination of its monomers, so aggregates need to be computed. We discuss the consequence of lowering comet crystal mass fractions by modeling IR SEDs with aggregates with crystals, and the implications for radial

  10. Simultaneous analysis of heparosan oligosaccharides by isocratic liquid chromatography with charged aerosol detection/mass spectrometry.

    PubMed

    Ji, Xiaohu; Hu, Guixin; Zhang, Qiongyan; Wang, Fengshan; Liu, Chunhui

    2016-11-01

    Uncovering the biological roles of heparosan oligosaccharides requires a simple and robust method for their separation and identification. We reported on systematic investigations of the retention behaviors of synthetic heparosan oligosaccharides on porous graphitic carbon (PGC) column by HPLC with charged aerosol detection. Oligosaccharides were strongly retained by PGC material in water-acetonitrile mobile phase, and eluted by trifluoroacetic acid occurring as narrow peaks. Addition of small fraction of methanol led to better selectivity of PGC to oligosaccharides than acetonitrile modifier alone, presumably, resulting from displacement of methanol to give different chemical environment at the PGC surface. Van't-Hoff plots demonstrated that retention behaviors highly depended on the column temperature and oligosaccharide moieties. By implementing the optimal MeOH content and temperature, a novel isocratic elution method was successfully developed for baseline resolution and identification of seven heparosan oligosaccharides using PGC-HPLC-CAD/MS. This approach allows for rapid analysis of heparosan oligosaccharides from various sources. PMID:27516280

  11. A Miniature System for Separating Aerosol Particles and Measuring Mass Concentrations

    PubMed Central

    Liang, Dao; Shih, Wen-Pin; Chen, Chuin-Shan; Dai, Chi-An

    2010-01-01

    We designed and fabricated a new sensing system which consists of two virtual impactors and two quartz-crystal microbalance (QCM) sensors for measuring particle mass concentration and size distribution. The virtual impactors utilized different inertial forces of particles in air flow to classify different particle sizes. They were designed to classify particle diameter, d, into three different ranges: d < 2.28 μm, 2.28 μm ≤ d ≤ 3.20 μm, d > 3.20 μm. The QCM sensors were coated with a hydrogel, which was found to be a reliable adhesive for capturing aerosol particles. The QCM sensor coated with hydrogel was used to measure the mass loading of particles by utilizing its characteristic of resonant frequency shift. An integrated system has been demonstrated. PMID:22319317

  12. Compositional and Optical Properties of Titan Haze Analogs Using Aerosol Mass Spectrometry, Photoacoustic Spectroscopy and Cavity Ring-Down Spectroscopy

    NASA Astrophysics Data System (ADS)

    Ugelow, M.; Zarzana, K. J.; Tolbert, M. A.

    2015-12-01

    The organic haze that surrounds Saturn's moon Titan is formed through the photolysis and electron initiated dissociation of methane and nitrogen. The chemical pathways leading to haze formation and the resulting haze optical properties are still highly uncertain. Here we examine the compositional and optical properties of Titan haze aerosol analogs. By studying these properties together, the impact of haze on Titan's radiative balance can be better understood. The aerosol analogs studied are produced from different initial methane concentrations (0.1, 2 and 10% CH4) using spark discharge excitation. To determine the complex refractive index of the aerosol, we combine two spectroscopic techniques, one that measures absorption and one that measures extinction: photoacoustic spectroscopy coupled with cavity ring-down spectroscopy (PASCaRD). This technique provides the benefit of a high precision determination of the imaginary component of the refractive index (k), along with the highly sensitive determination of the real component of the refractive index (n). The refractive indices are retrieved at two wavelengths, 405 and 532 nm, using the PASCaRD system. To yield aerosol composition, quadrupole aerosol mass spectrometry is used. Compositional information is obtained from a technique that uses isotopically labeled and unlabeled methane gas. I will present preliminary data on the complex refractive indices of Titan aerosol analogs at both wavelengths, in conjunction with the aerosol composition as a percent by weight of carbon, nitrogen and hydrogen. The correlation of optical and chemical properties should be useful for remote sensing instruments probing Titan haze.

  13. Real-Time Chemical Analysis of E-Cigarette Aerosols By Means Of Secondary Electrospray Ionization Mass Spectrometry.

    PubMed

    García-Gómez, Diego; Gaisl, Thomas; Barrios-Collado, César; Vidal-de-Miguel, Guillermo; Kohler, Malcolm; Zenobi, Renato

    2016-02-12

    Chemical analysis of aerosols collected from electronic cigarettes (ECs) has shown that these devices produce vapors that contain harmful and potentially harmful compounds. Conventional analytical methods used for the analysis of electronic cigarettes do not reflect the actual composition of the aerosols generated because they usually neglect the changes in the chemical composition that occur during the aerosol generation process and after collection. The aim of this work was to develop and apply a method for the real-time analysis of electronic cigarette aerosols, based on the secondary electrospray ionization technique coupled to high-resolution mass spectrometry, by mimicking the "vaping" process. Electronic cigarette aerosols were successfully analyzed and quantitative differences were found between the liquids and aerosols. Thanks to the high sensitivity shown by this method, more than 250 chemical substances were detected in the aerosols, some of them showing a high correlation with the operating power of the electronic cigarettes. The method also allows proper quantification of several chemical components such as alkaloids and flavor compounds.

  14. Determination of water-soluble and insoluble (dilute-HCl-extractable) fractions of Cd, Pb and Cu in Antarctic aerosol by square wave anodic stripping voltammetry: distribution and summer seasonal evolution at Terra Nova Bay (Victoria Land).

    PubMed

    Annibaldi, A; Truzzi, C; Illuminati, S; Bassotti, E; Scarponi, G

    2007-02-01

    Eight PM10 aerosol samples were collected in the vicinity of the "Mario Zucchelli" Italian Antarctic Station (formerly Terra Nova Bay Station) during the 2000-2001 austral summer using a high-volume sampler and precleaned cellulose filters. The aerosol mass was determined by differential weighing of filters carried out in a clean chemistry laboratory under controlled temperature and humidity. A two-step sequential extraction procedure was used to separate the water-soluble and the insoluble (dilute-HCl-extractable) fractions. Cd, Pb and Cu were determined in the two fractions using an ultrasensitive square wave anodic stripping voltammetric (SWASV) procedure set up for and applied to aerosol samples for the first time. Total extractable metals showed maxima at midsummer for Cd and Pb and a less clear trend for Cu. In particular, particulate metal concentrations ranged as follows: Cd 0.84-9.2 microg g(-1) (average 4.7 microg g(-1)), Pb 13.2-81 microg g(-1) (average 33 microg g(-1)), Cu 126-628 microg g(-1) (average 378 microg g(-1)). In terms of atmospheric concentration, the values were: Cd 0.55-6.3 pg m(-3) (average 3.4 pg m(-3)), Pb 8.7-48 pg m(-3) (average 24 pg m(-3)), Cu 75-365 pg m(-3) (average 266 pg m(-3)). At the beginning of the season the three metals appear widely distributed in the insoluble (HCl-extractable) fraction (higher proportions for Cd and Pb, 90-100%, and lower for Cu, 70-90%) with maxima in the second half of December. The soluble fraction then increases, and at the end of the season Cd and Pb are approximately equidistributed between the two fractions, while for Cu the soluble fraction reaches its maximum level of 36%. Practically negligible contributions are estimated for crustal and sea-spray sources. Low but significant volcanic contributions are estimated for Cd and Pb (approximately 10% and approximately 5%, respectively), while there is an evident although not quantified marine biogenic source, at least for Cd. The estimated natural

  15. DARK MATTER MASS FRACTION IN LENS GALAXIES: NEW ESTIMATES FROM MICROLENSING

    SciTech Connect

    Jiménez-Vicente, J.; Mediavilla, E.; Muñoz, J. A.

    2015-02-01

    We present a joint estimate of the stellar/dark matter mass fraction in lens galaxies and the average size of the accretion disk of lensed quasars based on microlensing measurements of 27 quasar image pairs seen through 19 lens galaxies. The Bayesian estimate for the fraction of the surface mass density in the form of stars is α = 0.21 ± 0.14 near the Einstein radius of the lenses (∼1-2 effective radii). The estimate for the average accretion disk size is R{sub 1/2}=7.9{sub −2.6}{sup +3.8}√(M/0.3 M{sub ⊙}) light days. The fraction of mass in stars at these radii is significantly larger than previous estimates from microlensing studies assuming quasars were point-like. The corresponding local dark matter fraction of 79% is in good agreement with other estimates based on strong lensing or kinematics. The size of the accretion disk inferred in the present study is slightly larger than previous estimates.

  16. Molecular composition of organic aerosols at urban background and road tunnel sites using ultra-high resolution mass spectrometry.

    PubMed

    Tong, Haijie; Kourtchev, Ivan; Pant, Pallavi; Keyte, Ian J; O'Connor, Ian P; Wenger, John C; Pope, Francis D; Harrison, Roy M; Kalberer, Markus

    2016-07-18

    Organic aerosol composition in the urban atmosphere is highly complex and strongly influenced by vehicular emissions which vary according to the make-up of the vehicle fleet. Normalized test measurements do not necessarily reflect real-world emission profiles and road tunnels are therefore ideal locations to characterise realistic traffic particle emissions with minimal interference from other particle sources and from atmospheric aging processes affecting their composition. In the current study, the composition of fine particles (diameter ≤2.5 μm) at an urban background site (Elms Road Observatory Site) and a road tunnel (Queensway) in Birmingham, UK, were analysed with direct infusion, nano-electrospray ionisation ultrahigh resolution mass spectrometry (UHRMS). The overall particle composition at these two sites is compared with an industrial harbour site in Cork, Ireland, with special emphasis on oxidised mono-aromatics, polycyclic aromatic hydrocarbons (PAHs) and nitro-aromatics. Different classification criteria, such as double bond equivalents, aromaticity index and aromaticity equivalent are used and compared to assess the fraction of aromatic components in the approximately one thousand oxidized organic compounds at the different sampling locations. PMID:27143100

  17. Propellant Mass Fraction Calculation Methodology for Launch Vehicles and Application to Ares Vehicles

    NASA Technical Reports Server (NTRS)

    Holt, James B.; Monk, Timothy S.

    2009-01-01

    Propellant Mass Fraction (pmf) calculation methods vary throughout the aerospace industry. While typically used as a means of comparison between candidate launch vehicle designs, the actual pmf calculation method varies slightly from one entity to another. It is the purpose of this paper to present various methods used to calculate the pmf of launch vehicles. This includes fundamental methods of pmf calculation that consider only the total propellant mass and the dry mass of the vehicle; more involved methods that consider the residuals, reserves and any other unusable propellant remaining in the vehicle; and calculations excluding large mass quantities such as the installed engine mass. Finally, a historical comparison is made between launch vehicles on the basis of the differing calculation methodologies, while the unique mission and design requirements of the Ares V Earth Departure Stage (EDS) are examined in terms of impact to pmf.

  18. Eliminating mass-fractionation effects on U-Pb isochron ages without double spiking

    NASA Astrophysics Data System (ADS)

    Ludwig, Kenneth R.

    2001-09-01

    The utility of uranium-lead isochrons for dating rocks with a restricted range in U/Pb is limited by any uncertainty in the mass fractionation of the analysis. Double spiking (TIMS) or thallium normalization (ICP-MS) remove much of this limitation, as does the method of Getty and DePaolo (1995) for very young rocks. Optimal use of the 3-D "Total Pb/U isochron," however, is extremely simple to apply, requires only single-spiked TIMS analyses, and essentially eliminates fractionation-related age imprecision for rocks of any age.

  19. Stochastic resonance in a fractional harmonic oscillator subject to random mass and signal-modulated noise

    NASA Astrophysics Data System (ADS)

    Guo, Feng; Zhu, Cheng-Yin; Cheng, Xiao-Feng; Li, Heng

    2016-10-01

    Stochastic resonance in a fractional harmonic oscillator with random mass and signal-modulated noise is investigated. Applying linear system theory and the characteristics of the noises, the analysis expression of the mean output-amplitude-gain (OAG) is obtained. It is shown that the OAG varies non-monotonically with the increase of the intensity of the multiplicative dichotomous noise, with the increase of the frequency of the driving force, as well as with the increase of the system frequency. In addition, the OAG is a non-monotonic function of the system friction coefficient, as a function of the viscous damping coefficient, as a function of the fractional exponent.

  20. Galaxy Cluster Gas Mass Fractions From Sunyaev-Zeldovich Effect Measurements: Constraints on Omega(M)

    NASA Technical Reports Server (NTRS)

    Grego, Laura; Carlstrom, John E.; Reese, Erik D.; Holder, Gilbert P.; Holzapfel, William L.; Joy, Marshall K.; Mohr, Joseph J.; Patel, Sandeep

    2001-01-01

    Using sensitive centimeter-wave receivers mounted on the Owens Valley Radio Observatory and Berkeley-Illinois-Maryland-Association millimeter arrays, we have obtained interferometric measurements of the Sunyaev-Zeldovich(SZ) effect toward massive galaxy clusters. We use the SZ data to determine the pressure distribution of the cluster gas and, in combination with published X-ray temperatures, to infer the gas mass and total gravitational mass of 18 clusters. The gas mass fraction, f(g), is calculated for each cluster and is extrapolated to the fiducial radius r(500) using the results of numerical simulations. The mean f(g) within r(500) is 0.081(+ 0.009 / - 0.011) per h(100) (statistical uncertainty at 68% confidence level, assuming Omega(M) = 0.3, Omega(Lambda) = 0.7). We discuss possible sources of systematic errors in the mean f(sub g) measurement. We derive an upper limit for Omega(M) from this sample under the assumption that the mass composition of clusters within r(500) reflects the universal mass composition: Omega(M)h is less than or equal to Omega(B)/f(g). The gas mass fractions depend on cosmology through the angular diameter distance and the r(500) correction factors. For a flat universe (Omega(Lambda) is identical with 1 - Omega(M)) and h = 0.7, we find the measured gas mass fractions are consistent with Omega(M) is less than 0.40, at 68% confidence. Including estimates of the baryons contained in galaxies and the baryons which failed to become bound during the cluster formation process, we find Omega(M) is approximately equal to 0.25.

  1. ORIGINS OF NON-MASS-DEPENDENT FRACTIONATION OF EXTRA-TERRESTRIAL OXYGEN

    SciTech Connect

    Barcena, Homar; Connolly, Harold C.

    2012-08-01

    The distribution of oxygen isotopes in meteorites and within the earliest solids that formed in the solar system hints that the precursors of these materials must have undergone a mass-independent process. The mass-independent process is specifically one that fractionates {sup 16}O from {sup 17}O and {sup 18}O. This chemical signature is indicative of non-equilibrium processing, which bear resemblance to some unusual terrestrial phenomenon such as fractionation of ozone in the upper Earth atmosphere. That the mass-independent fractionation of oxygen isotopes is preserved within petrological records presents planetary scientists interesting clues to the events that may have occurred during the formation of the solar system. Currently, there are several hypotheses on the origins of the oxygen isotope distribution within primitive planetary materials, which include both thermal and photochemical models. We present a new model based on a physico-chemical hypothesis for the origin of non-mass-dependent O-isotope distribution in oxygen-bearing extra-terrestrial materials, which originated from the disproportionation of CO in dark molecular clouds to create CO{sub 2} reservoirs. The disproportionation created a reservoir of heavy oxygen isotopes and could have occurred throughout the evolution of the disk. The CO{sub 2} was a carrier of the isotope anomaly in the solar nebula and we propose that non-steady-state mixing of these reservoirs with the early rock-forming materials during their formation corresponds with the birth and evolution of the solar system.

  2. 40 CFR Table 4 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Default Organic HAP Mass Fraction for... OOOO of Part 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass... organic HAP, percent by mass 1. Toluene 108-88-3 1.0 Toluene. 2. Xylene(s) 1330-20-7 1.0...

  3. 40 CFR Table 4 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Default Organic HAP Mass Fraction for... OOOO of Part 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass... organic HAP, percent by mass 1. Toluene 108-88-3 1.0 Toluene. 2. Xylene(s) 1330-20-7 1.0...

  4. 40 CFR Table 4 to Subpart Oooo of... - Default Organic HAP Mass Fraction for Solvents and Solvent Blends

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Default Organic HAP Mass Fraction for... OOOO of Part 63—Default Organic HAP Mass Fraction for Solvents and Solvent Blends You may use the mass... organic HAP, percent by mass 1. Toluene 108-88-3 1.0 Toluene. 2. Xylene(s) 1330-20-7 1.0...

  5. Mass Spectra of Individual Aerosol Particles Acquired During Intercepts of a Space Shuttle Exhaust Plume

    NASA Astrophysics Data System (ADS)

    Cziczo, D. J.; Cziczo, D. J.; Murphy, D. M.; Thomson, D. S.; Thomson, D. S.

    2001-12-01

    The WB-57 aircraft accomplished fourteen distinct stratospheric intercepts of the exhaust plume from a space shuttle during ACCENT 2000. Liftoff of the shuttle Atlantis for STS-106 occurred at 8:46 am local (12:46 UTC) with intercepts occurring from 5 to 90 minutes afterward. The Particle Analysis by Laser Mass Spectrometry (PALMS) instrument, mounted in the nose of the aircraft, was used to acquire individual mass spectra of over 2500 particles during these intercepts. The majority of positive mass spectra indicate the presence of the metals Al, Fe, Zn, Ga, and V, all components found in the solid rocket fuel. Organic material, presumably from binding and curing agents, was also present. Negative mass spectra showed Cl from the oxidizer, ammonium perchlorate, as well as water. Rare exotic particles, for example those containing Ti and Ag and possibly formed during engine or seal ablation, were also detected. Particles originating from shuttle exhaust but also containing significant sulfuric acid were common toward the outer edge of the plume, especially during late encounters, suggesting that deposition or aerosol collision had occurred.

  6. High-Resolution Mass Spectrometric Analysis of Secondary Organic Aerosol Produced by Ozonation of Limonene

    SciTech Connect

    Walser, Maggie L.; Dessiaterik, Yury; Laskin, Julia; Laskin, Alexander; Nizkorodov, Serguei

    2008-02-08

    Secondary organic aerosol (SOA) particles formed from the ozone-initiated oxidation of limonene are characterized by high-resolution electrospray ionization mass spectrometry in both the positive and negative ion modes. The mass spectra reveal a large number of both monomeric (m/z < 300) and oligomeric (m/z > 300) products of oxidation. A combination of high resolving power (m/Δm ~60,000) and Kendrick mass defect analysis makes it possible to unambiguously determine the composition for hundreds of individual compounds in SOA samples. Van Krevelen analysis shows that the SOA compounds are heavily oxidized, with average O:C ratios of 0.43 and 0.50 determined from the positive and negative ion mode spectra, respectively. An extended reaction mechanism for the formation of the first generation SOA molecular components is proposed. The mechanism includes known isomerization and addition reactions of the carbonyl oxide intermediates generated during the ozonation of limonene, and numerous isomerization pathways for alkoxy radicals resulting from the decomposition of unstable carbonyl oxides. The isomerization reactions yield numerous products with a progressively increasing number of alcohol and carbonyl groups, whereas C-C bond scission reactions in alkoxy radicals shorten the carbon chain. Together these reactions yield a large number of isomeric products with broadly distributed masses. A qualitative agreement is found between the number and degree of oxidation of the predicted and measured reaction products in the monomer range.

  7. The real part of the refractive indices and effective densities for chemically segregated ambient aerosols in Guangzhou by a single particle aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Zhang, G.; Bi, X.; Qiu, N.; Han, B.; Lin, Q.; Peng, L.; Chen, D.; Wang, X.; Peng, P.; Sheng, G.; Zhou, Z.

    2015-12-01

    Microphysical properties of atmospheric aerosols are essential to better evaluate their radiative forcing. This paper first presents an estimate of the real part of the refractive indices (n) and effective densities (ρeff) of chemically segregated atmospheric aerosols in China. Vacuum aerodynamic diameter, chemical compositions, and light scattering intensities of individual particles were simultaneously measured by a single particle aerosol mass spectrometer (SPAMS) during fall of 2012 in Guangzhou. On the basis of Mie theory, n and ρeff were estimated for 17 particle types in four categories: organics (OC), elemental carbon (EC), internally mixed EC and OC (ECOC), and metal rich, respectively. Results indicate the presence of spherical or nearly spherical shape for majority of particle types, whose partial scattering cross section vs. sizes were well fitted to Mie theoretical modeling results. While sharing n in a narrow range (1.47-1.53), majority of particle types exhibited a wide range of ρeff (0.87-1.51 g cm-3). OC group is associated with the lowest ρeff (0.87-1.07 g cm-3), while metal rich group with the highest ones (1.29-1.51 g cm-3). It is noteworthy that a specific EC type exhibits a complex scattering curve vs. size due to the presence of both compact and irregularly shape particles. Overall, the results on detailed relationship between physical and chemical properties benefits future researches on the impact of aerosols on visibility and climate.

  8. Fractal morphology, imaging and mass spectrometry of single aerosol particles in flight.

    PubMed

    Loh, N D; Hampton, C Y; Martin, A V; Starodub, D; Sierra, R G; Barty, A; Aquila, A; Schulz, J; Lomb, L; Steinbrener, J; Shoeman, R L; Kassemeyer, S; Bostedt, C; Bozek, J; Epp, S W; Erk, B; Hartmann, R; Rolles, D; Rudenko, A; Rudek, B; Foucar, L; Kimmel, N; Weidenspointner, G; Hauser, G; Holl, P; Pedersoli, E; Liang, M; Hunter, M S; Hunter, M M; Gumprecht, L; Coppola, N; Wunderer, C; Graafsma, H; Maia, F R N C; Ekeberg, T; Hantke, M; Fleckenstein, H; Hirsemann, H; Nass, K; White, T A; Tobias, H J; Farquar, G R; Benner, W H; Hau-Riege, S P; Reich, C; Hartmann, A; Soltau, H; Marchesini, S; Bajt, S; Barthelmess, M; Bucksbaum, P; Hodgson, K O; Strüder, L; Ullrich, J; Frank, M; Schlichting, I; Chapman, H N; Bogan, M J

    2012-06-28

    The morphology of micrometre-size particulate matter is of critical importance in fields ranging from toxicology to climate science, yet these properties are surprisingly difficult to measure in the particles' native environment. Electron microscopy requires collection of particles on a substrate; visible light scattering provides insufficient resolution; and X-ray synchrotron studies have been limited to ensembles of particles. Here we demonstrate an in situ method for imaging individual sub-micrometre particles to nanometre resolution in their native environment, using intense, coherent X-ray pulses from the Linac Coherent Light Source free-electron laser. We introduced individual aerosol particles into the pulsed X-ray beam, which is sufficiently intense that diffraction from individual particles can be measured for morphological analysis. At the same time, ion fragments ejected from the beam were analysed using mass spectrometry, to determine the composition of single aerosol particles. Our results show the extent of internal dilation symmetry of individual soot particles subject to non-equilibrium aggregation, and the surprisingly large variability in their fractal dimensions. More broadly, our methods can be extended to resolve both static and dynamic morphology of general ensembles of disordered particles. Such general morphology has implications in topics such as solvent accessibilities in proteins, vibrational energy transfer by the hydrodynamic interaction of amino acids, and large-scale production of nanoscale structures by flame synthesis.

  9. Fractal morphology, imaging and mass spectrometry of single aerosol particles in flight.

    PubMed

    Loh, N D; Hampton, C Y; Martin, A V; Starodub, D; Sierra, R G; Barty, A; Aquila, A; Schulz, J; Lomb, L; Steinbrener, J; Shoeman, R L; Kassemeyer, S; Bostedt, C; Bozek, J; Epp, S W; Erk, B; Hartmann, R; Rolles, D; Rudenko, A; Rudek, B; Foucar, L; Kimmel, N; Weidenspointner, G; Hauser, G; Holl, P; Pedersoli, E; Liang, M; Hunter, M S; Hunter, M M; Gumprecht, L; Coppola, N; Wunderer, C; Graafsma, H; Maia, F R N C; Ekeberg, T; Hantke, M; Fleckenstein, H; Hirsemann, H; Nass, K; White, T A; Tobias, H J; Farquar, G R; Benner, W H; Hau-Riege, S P; Reich, C; Hartmann, A; Soltau, H; Marchesini, S; Bajt, S; Barthelmess, M; Bucksbaum, P; Hodgson, K O; Strüder, L; Ullrich, J; Frank, M; Schlichting, I; Chapman, H N; Bogan, M J

    2012-06-28

    The morphology of micrometre-size particulate matter is of critical importance in fields ranging from toxicology to climate science, yet these properties are surprisingly difficult to measure in the particles' native environment. Electron microscopy requires collection of particles on a substrate; visible light scattering provides insufficient resolution; and X-ray synchrotron studies have been limited to ensembles of particles. Here we demonstrate an in situ method for imaging individual sub-micrometre particles to nanometre resolution in their native environment, using intense, coherent X-ray pulses from the Linac Coherent Light Source free-electron laser. We introduced individual aerosol particles into the pulsed X-ray beam, which is sufficiently intense that diffraction from individual particles can be measured for morphological analysis. At the same time, ion fragments ejected from the beam were analysed using mass spectrometry, to determine the composition of single aerosol particles. Our results show the extent of internal dilation symmetry of individual soot particles subject to non-equilibrium aggregation, and the surprisingly large variability in their fractal dimensions. More broadly, our methods can be extended to resolve both static and dynamic morphology of general ensembles of disordered particles. Such general morphology has implications in topics such as solvent accessibilities in proteins, vibrational energy transfer by the hydrodynamic interaction of amino acids, and large-scale production of nanoscale structures by flame synthesis. PMID:22739316

  10. Cluster mass fraction and size distribution determined by fs-time-resolved measurements

    NASA Astrophysics Data System (ADS)

    Gao, Xiaohui; Wang, Xiaoming; Shim, Bonggu; Arefiev, Alexey; Tushentsov, Mikhail; Breizman, Boris; Downer, Mike

    2009-11-01

    Characterization of supersonic gas jets is important for accurate interpretation and control of laser-cluster experiments. While average size and total atomic density can be found by standard Rayleigh scatter and interferometry, cluster mass fraction and size distribution are usually difficult to measure. Here we determine the cluster fraction and the size distribution with fs-time-resolved refractive index and absorption measurements in cluster gas jets after ionization and heating by an intense pump pulse. The fs-time-resolved refractive index measured with frequency domain interferometer (FDI) shows different contributions from monomer plasma and cluster plasma in the time domain, enabling us to determine the cluster fraction. The fs-time-resolved absorption measured by a delayed probe shows the contribution from clusters of various sizes, allowing us to find the size distribution.

  11. Tropospheric Aerosols

    NASA Astrophysics Data System (ADS)

    Buseck, P. R.; Schwartz, S. E.

    2003-12-01

    m, PM10=1.1 μg m-3; estimated coefficient of light scattering by particulate matter, σep, at 570 nm=12 Mm-1). (b) High aerosol concentration (PM2.5=43.9 μg m-3; PM10=83.4 μg m-3; estimated σep at 570 nm=245 Mm-1) (reproduced by permission of National Park Service, 2002). Although comprising only a small fraction of the mass of Earth's atmosphere, aerosol particles are highly important constituents of the atmosphere. Special interest has focused on aerosols in the troposphere, the lowest part of the atmosphere, extending from the land or ocean surface typically to ˜8 km at high latitudes, ˜12 km in mid-latitudes, and ˜16 km at low latitudes. That interest arises in large part because of the importance of aerosol particles in geophysical processes, human health impairment through inhalation, environmental effects through deposition, visibility degradation, and influences on atmospheric radiation and climate.Anthropogenic aerosols are thought to exert a substantial influence on Earth's climate, and the need to quantify this influence has sparked much of the current interest in and research on tropospheric aerosols. The principal mechanisms by which aerosols influence the Earth radiation budget are scattering and absorbing solar radiation (the so-called "direct effects") and modifying clouds and precipitation, thereby affecting both radiation and hydrology (the so-called "indirect effects"). Light scattering by aerosols increases the brightness of the planet, producing a cooling influence. Light-absorbing aerosols such as black carbon exert a warming influence. Aerosols increase the reflectivity of clouds, another cooling influence. These radiative influences are quantified as forcings, where a forcing is a perturbation to the energy balance of the atmosphere-Earth system, expressed in units of watts per square meter, W m-2. A warming influence is denoted a positive forcing, and a cooling influence, negative. The radiative direct and indirect forcings by

  12. Characterisation of lipid fraction of marine macroalgae by means of chromatography techniques coupled to mass spectrometry.

    PubMed

    Ragonese, Carla; Tedone, Laura; Beccaria, Marco; Torre, Germana; Cichello, Filomena; Cacciola, Francesco; Dugo, Paola; Mondello, Luigi

    2014-02-15

    In this work the characterisation of the lipid fraction of several species of marine macro algae gathered along the eastern coast of Sicily is reported. Two species of green marine algae (Chloropyceae), two species of red marine algae (Rhodophyceae) and four species of brown marine algae (Pheophyceae) were evaluated in terms of fatty acids, triacylglycerols, pigments and phospholipids profile. Advanced analytical techniques were employed to fully characterise the lipid profile of these Mediterranean seaweeds, such as GC-MS coupled to a novel mass spectra database supported by the simultaneous use of linear retention index (LRI) for the identification of fatty acid profile; LC-MS was employed for the identification of triacylglycerols (TAGs), carotenoids and phospholipids; the determination of accurate mass was carried out on carotenoids and phospholipids. Quantitative data are reported on fatty acids and triacylglycerols as relative percentage of total fraction. PMID:24128566

  13. Element composition of insoluble fraction of aerosols in snow in the vicinity of oil chemistry refinery (Pavlodar City, Kazakhstan) and petrochemical plant (Tomsk City, Russia)

    NASA Astrophysics Data System (ADS)

    Talovskaya, Anna V.; Filimonenko, Ekaterina A.; Yazikov, Egor G.; Shakhova, Tatyana S.; Parygina, Irina A.

    2015-11-01

    Tomsk petrochemical plant (Russia) and Pavlodar oil chemistry refinery (Kazakhstan) are the sources of air contamination in Tomsk and Pavlodar respectively. Therefore, it is very important to study the level of air contamination with particulate matter as well as ultimate composition of these particles. Disposable solid particles fall out to the snow cover, so snow is an accumulator of the particles. The article deals with the study results of dust load and concentrations of Br, Sb, La, Ce, Sm and Nd in insoluble fraction of aerosols in snow in the vicinity of Pavlodar oil chemistry refinery and Tomsk petrochemical plant. The instrumental neutron activation analysis was used for the ultimate composition detection. Results were shown that the dust load in the vicinity of Tomsk petrochemical plant is higher than in Pavlodar. We have detected high concentrations of La, Br and Sm in insoluble fraction of aerosols in snow in the vicinity of Pavlodar refinery and high concentrations of Sb and Ce in Tomsk. Moreover, we have detected high Br concentration in insoluble fraction of aerosols in snow of the vicinity of both plants. Gas burning on the flares of these enterprises is likely a potential source of Br. La to light lanthanoids ratio have shown La is of anthropogenic origin. In addition, enrichment factor estimation reflects an anthropogenic origin of La, Sm, Br, Ce and Sb as well. These elements might be emitted from different production facilities of the plants.

  14. Probing Molecular Associations of Secondary Organic Aerosol (SOA) Samples from CalNex 2010 with Nano-DESI High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    O'Brien, R. E.; Nguyen, T. B.; Laskin, A.; Laskin, J.; Hayes, P. L.; Liu, S.; Jimenez, J. L.; Russell, L. M.; Nizkorodov, S.; Goldstein, A. H.

    2012-12-01

    This project focuses on analyzing the identities of molecules that comprise oligomers in size resolved aerosol fractions. Since oligomers are generally too large and polar to be measured by typical GC/MS analysis, soft ionization with high resolution mass spectrometry is used to extend the range of observable compounds. Samples collected during CalNex 2010 in Bakersfield and Los Angeles and secondary organic aerosol (SOA) produced in a photochemical chamber by photooxidation of diesel (DSL) fuel and isoprene (ISO) under humid, high-NOx conditions have been analyzed with nanospray desorption electrospray ionization (nano-DESI) and a high-resolution Orbitrap mass spectrometer. The nano-DESI is a soft ionization technique that allows molecular ions to be observed and the Orbitrap has sufficient resolution to determine the elemental composition of almost all species above the detection limit. A large fraction of SOA is made up of high molecular weight oligomers which are thought to form through acid catalyzed reactions of photo-chemically processed volatile organic compounds (VOC). The formation of oligomers is influenced by the VOCs available, the amount of atmospheric sulfate and nitrate, and the magnitude of photo-chemical processing, among other potential influences. We present the elemental composition of chemical species in size resolved SOA samples with six-hour time resolution, providing the first time resolved data set for the study of these oligomers in atmospheric samples. We present a comparison of the degree of overlap between the ambient and chamber experiments as a novel method to examine sources for this fraction of SOA. Possible formation pathways and sources of observed compounds are analyzed by comparison to other concurrent measurements at the site.

  15. 40 CFR Table 6 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Petroleum Solvent Groups a 6 Table 6 to Subpart QQQQ of Part 63 Protection of Environment ENVIRONMENTAL...—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in... Spirits, Petroleum Spirits, Petroleum Oil, Petroleum Naphtha, Solvent Naphtha, Solvent Blend. c...

  16. 40 CFR Table 4 to Subpart Rrrr of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups 1

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Petroleum Solvent Groups 1 4 Table 4 to Subpart RRRR of Part 63 Protection of Environment ENVIRONMENTAL... Organic HAP Mass Fraction for Petroleum Solvent Groups 1 You May Use the Mass Fraction Values in the..., Petroleum Spirits, Petroleum Oil, Petroleum Naphtha, Solvent Naphtha, Solvent Blend. 3 E.g.,...

  17. 40 CFR Table 6 to Subpart Qqqq of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Petroleum Solvent Groups a 6 Table 6 to Subpart QQQQ of Part 63 Protection of Environment ENVIRONMENTAL... HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction values in the following..., Petroleum Spirits, Petroleum Oil, Petroleum Naphtha, Solvent Naphtha, Solvent Blend. c E.g.,...

  18. 40 CFR Table 4 to Subpart Pppp of... - Default Organic HAP Mass Fraction for Petroleum Solvent Groups a

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Petroleum Solvent Groups a 4 Table 4 to Subpart PPPP of Part 63 Protection of Environment ENVIRONMENTAL... 63—Default Organic HAP Mass Fraction for Petroleum Solvent Groups a You may use the mass fraction... Hydrocarbon, Aliphatic Naphtha, Naphthol Spirits, Petroleum Spirits, Petroleum Oil, Petroleum Naphtha,...

  19. Initial characterization of micafungin pulmonary delivery via two different nebulizers and multivariate data analysis of aerosol mass distribution profiles.

    PubMed

    Shi, Shuai; Ashley, Elizabeth S Dodds; Alexander, Barbara D; Hickey, Anthony J

    2009-01-01

    Pharmaceutical aerosols have been targeted to the lungs for the treatment of asthma and pulmonary infectious diseases successfully. Micafungin (Astellas Pharma US, Deerfield, IL, USA) has been shown to be an effective antifungal agent when administrated intravenously. Pulmonary delivery of micafungin has not previously been reported. In the present pilot study, we characterize the performance of two nebulizers and their potential for delivering micafungin to the lungs as well as the use of multivariate data analysis for mass distribution profile comparison. The concentration of micafungin sodium increased by 21% when delivered by the Acorn II nebulizer and by 20% when delivered by the LC Plus nebulizer, respectively, from the first to the second sampling period. The Acorn II nebulizer delivered a fine particle fraction FPF(5.8) (%<5.8 microm) of 92.5 +/- 0.8 and FPF(3.3) (%<3.3 microm) of 82.3 +/- 2.1 during the first sampling period. For the LC Plus nebulizer, FPF(5.8) was 92.3 +/- 0.1 and FPF(3.3) was 67.0 +/- 0.7 during the first sampling period. The mass median aerodynamic diameter (MMAD) increased from 1.67 +/- 0.05 to 1.77 +/- 0.04 mum (Acorn II nebulizer) and from 2.09 +/- 0.01 to 2.20 +/- 0.01 microm (Pari LC Plus nebulizer) from the first to the second sampling periods. These changes in MMAD were statistically significant by paired t test. Multivariate data analysis showed that this could be explained systematically by greater drug deposition on stages with larger cutoff sizes and reduced drug deposition on stages with smaller cutoff sizes rather than multimodal deposition or other anomalies in size distribution.

  20. Pattern of aerosol mass loading and chemical composition over the atmospheric environment of an urban coastal station

    NASA Astrophysics Data System (ADS)

    Bindu, G.; Nair, Prabha R.; Aryasree, S.; Hegde, Prashant; Jacob, Salu

    2016-02-01

    Aerosol sampling was carried out at four locations in and around Cochin (9°58‧ N, 76°17‧ E), an urban area, located on the southwest coast of India. The gravimetric estimates of aerosol mass loading showed wide range from 78 μg m-3 to >450 μg m-3, occasionally reaching values >500 μg m-3, associated with regional source characteristics. Most of the values were above the air quality standard. Both boundary layer and synoptic scale airflow pattern play role in the temporal features in aerosol mass loading and chemical composition. Chemical analysis of the aerosol samples were done for anionic species viz; F-, Cl-, Br-, NO2-,   NO3-,   PO43-,   SO42- and metallic/cationic species viz; Na, Ca, K, Mg, NH4+, Fe, Al, Cu, Mg, Pb, etc using Ion Chromatography, Atomic Absorption Spectroscopy (AAS) and Inductively Coupled Plasma- Atomic Emission Spectroscopy (ICP-AES). At all the locations, extremely high mass concentration of SO42- was observed with the mean value of 13±6.4 μg m-3 indicating the strong anthropogenic influence. Statistical analysis of the chemical composition data was carried out and the principal factors presented. Seasonal variation of these chemical species along with their percentage contributions and regional variations were also examined. Increase in level of Na in aerosol samples indicated the influence of monsoonal activity. Most of the species showed mass concentrations well above those measured over another coastal site Thiruvananthapuram (8°29‧ N, 76°57‧ E) situated ~220 km south of Cochin revealing the highly localized aerosol features.

  1. Molecular Characterization of Organic Aerosols Using Nanospray Desorption/Electrospray Ionization-Mass Spectrometry

    SciTech Connect

    Roach, Patrick J.; Laskin, Julia; Laskin, Alexander

    2010-10-01

    Nanospray desorption electrospray ionization (Nano-DESI) combined with high-resolution mass spectrometry (HR/MS) is a promising approach for detailed chemical characterization of atmospheric organic aerosol (OA) collected in laboratory and field experiments. In Nano-DESI analyte is desorbed into a solvent bridge formed between two capillaries and the analysis surface, which enables fast and efficient characterization of OA collected on substrates without special sample preparation. Stable signals achieved using Nano-DESI make it possible to obtain high-quality HR/MS data using only a small amount of material (<10 ng). Furthermore, Nano-DESI enables efficient detection of chemically labile compounds in OA, which is important for understanding chemical aging phenomena.

  2. On the conversion of tritium units to mass fractions for hydrologic applications

    USGS Publications Warehouse

    Stonestrom, David A.; Andraski, Brain J.; Cooper, Clay A.; Mayers, Charles J.; Michel, Robert L.

    2013-01-01

    We develop a general equation for converting laboratory-reported tritium levels, expressed either as concentrations (tritium isotope number fractions) or mass-based specific activities, to mass fractions in aqueous systems. Assuming that all tritium is in the form of monotritiated water simplifies the derivation and is shown to be reasonable for most environmental settings encountered in practice. The general equation is nonlinear. For tritium concentrations c less than 4.5×1012 tritium units (TU) - i.e. specific tritium activities11 Bq kg-1 - the mass fraction w of tritiated water is approximated to within 1 part per million by w ≈ c×2.22293×10-18, i.e. the conversion is linear for all practical purposes. Terrestrial abundances serve as a proxy for non-tritium isotopes in the absence of sample-specific data. Variation in the relative abundances of non-tritium isotopes in the terrestrial hydrosphere produces a minimum range for the mantissa of the conversion factor of [2.22287; 2.22300].

  3. Proteomic investigation of natural killer cell microsomes using gas-phase fractionation by mass spectrometry.

    PubMed

    Blonder, Josip; Rodriguez-Galan, Maria Cecilia; Lucas, David A; Young, Howard A; Issaq, Haleem J; Veenstra, Timothy D; Conrads, Thomas P

    2004-04-01

    We have explored the utility of gas-phase fractionation by mass spectrometry (MS) in the mass-to-charge (m/z) dimension (GPF(m/z)) for increasing the effective number of protein identifications in cases where sample quantity limits the use of multi-dimensional chromatographic fractionation. A peptide digestate from proteins isolated from the membrane fraction of natural killer (NK) cells was analyzed by microcapillary reversed-phase liquid chromatography coupled online to an ion-trap (IT) mass spectrometer. Performing GPF(m/z) using eight narrow precursor ion scan m/z ranges enabled the identification of 340 NK cell proteins from 12 microg of digestate, representing more than a fivefold increase in the number of proteins identified as compared to the same experiment employing a standard precursor ion survey scan m/z range (i.e., m/z 400-2000). The results show that GPF(m/z) represents an effective technique for increasing protein identifications in global proteomic investigations especially when sample quantity is limited.

  4. Fraction collection in capillary electrophoresis for various stand-alone mass spectrometers.

    PubMed

    Helmja, Kati; Borissova, Maria; Knjazeva, Tatjana; Jaanus, Martin; Muinasmaa, Urmas; Kaljurand, Mihkel; Vaher, Merike

    2009-04-24

    A procedure for collecting fractions during capillary electrophoresis for their analysis using various stand-alone instruments is described. The results of a systematic study of the optimization and application of capillary electrophoresis (CE) in conjunction with a reverse-phase high-performance liquid chromatography electrospray ionization quadrupole time of flight-tandem mass spectrometry (RP-HPLC-ESI-Q-TOF-MS/MS) and inductively-coupled mass spectrometry (ICP-MS) to the analysis of the seed extract of the Japanese Pagoda Tree (Sophora japonica) are presented. The off-line coupling of CE to the matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS) for the proteins mixture was applied. The cathode end of the capillary was placed inside a stainless steel needle using a coaxial liquid-sheath-flow configuration. The optimization of experimental parameters resulted in an efficient methodology for MS analysis of fractions. Several components contained in the extract of S. japonica were identified, some not previously known. It was demonstrated that low sensitivity, which is a real problem in off-line CE-MS analysis, could be tolerated because of a more flexible optimization of the CE separation conditions and the choice of independent stand-alone instruments for analysis of separated fractions. The estimated limit of detection for CE-RP-HPLC-ESI-Q-TOF-MS was 50 microM of polyphenols and for CE-ICP-MS, 1-100 microg/l. PMID:19147148

  5. Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

    USGS Publications Warehouse

    Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.

    2013-01-01

    As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

  6. Mexico City aerosol analysis during MILAGRO using high resolution aerosol mass spectrometry at the urban supersite (T0) - Part 1: Fine particle composition and organic source apportionment

    SciTech Connect

    Aiken, A.C.; Wang, J.; Salcedo, D.; Cubison, M. J.; Huffman, J. A.; DeCarlo, P. F.; Ulbrich, I. M.; Docherty, K. S.; Sueper, D.; Kimmel, J. R.; Worsnop, D. R.; Trimborn, A.; Northway, M.; Stone, E. A.; Schauer, J. J.; Volkamer, R. M.; Fortner, E.; de Foy, B.; Laskin, A.; Shutthanandan, V.; Zheng, J.; Zhang, R.; Gaffney, J.; Marley, N. A.; Paredes-Miranda, G.; Arnott, W. P.; Molina, L. T.; Sosa, G.; Jimenez, J. L.

    2009-09-01

    Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and complementary instrumentation. Mass concentrations, diurnal cycles, and size distributions of inorganic and organic species are similar to results from the CENICA supersite in April 2003 with organic aerosol (OA) comprising about half of the fine PM mass. Positive Matrix Factorization (PMF) analysis of the high resolution OA spectra identified three major components: chemically-reduced urban primary emissions (hydrocarbon-like OA, HOA), oxygenated OA (OOA, mostly secondary OA or SOA), and biomass burning OA (BBOA) that correlates with levoglucosan and acetonitrile. BBOA includes several very large plumes from regional fires and likely also some refuse burning. A fourth OA component is a small local nitrogen-containing reduced OA component (LOA) which accounts for 9% of the OA mass but one third of the organic nitrogen, likely as amines. OOA accounts for almost half of the OA on average, consistent with previous observations. OA apportionment results from PMF-AMS are compared to the PM{sub 2.5} chemical mass balance of organic molecular markers (CMB-OMM, from GC/MS analysis of filters). Results from both methods are overall consistent. Both assign the major components of OA to primary urban, biomass burning/woodsmoke, and secondary sources at similar magnitudes. The 2006 Mexico City emissions inventory underestimates the urban primary PM{sub 2.5} emissions by a factor of {approx}4, and it is {approx}16 times lower than afternoon concentrations when secondary species are included. Additionally, the forest fire contribution is at least an order-of-magnitude larger than in the inventory.

  7. Chemical composition, sources, and processes of urban aerosols during summertime in northwest China: insights from high-resolution aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Xu, J.; Zhang, Q.; Chen, M.; Ge, X.; Ren, J.; Qin, D.

    2014-12-01

    An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed along with a scanning mobility particle sizer (SMPS) and a multi-angle absorption photometer (MAAP) to measure the temporal variations of the mass loading, chemical composition, and size distribution of submicron particulate matter (PM1) in Lanzhou, northwest China, during 11 July-7 August 2012. The average (PM1 mass concentration including non-refractory (PM1 (NR-(PM1) measured by HR-ToF-AMS and black carbon (BC) measured by MAAP during this study was 24.5 μg m-3 (ranging from 0.86 to 105 μg m-3), with a mean composition consisting of 47% organics, 16% sulfate, 12% BC, 11% ammonium, 10% nitrate, and 4% chloride. Organic aerosol (OA) on average consisted of 70% carbon, 21% oxygen, 8% hydrogen, and 1% nitrogen, with the average oxygen-to-carbon ratio (O / C) of 0.33 and organic mass-to-carbon ratio (OM / OC) of 1.58. Positive matrix factorization (PMF) of the high-resolution organic mass spectra identified four distinct factors which represent, respectively, two primary OA (POA) emission sources (traffic and food cooking) and two secondary OA (SOA) types - a fresher, semi-volatile oxygenated OA (SV-OOA) and a more aged, low-volatility oxygenated OA (LV-OOA). Traffic-related hydrocarbon-like OA (HOA) and BC displayed distinct diurnal patterns, both with peak at ~ 07:00-11:00 (BJT: UTC +8), corresponding to the morning rush hours, while cooking-emission related OA (COA) peaked during three meal periods. The diurnal profiles of sulfate and LV-OOA displayed a broad peak between ~ 07:00 and 15:00, while those of nitrate, ammonium, and SV-OOA showed a narrower peak between ~ 08:00-13:00. The later morning and early afternoon maximum in the diurnal profiles of secondary aerosol species was likely caused by downward mixing of pollutants aloft, which were likely produced in the residual layer decoupled from the boundary layer during nighttime. The mass spectrum of SV-OOA was

  8. Evaluation of the Mg doping approach for Si mass fractionation correction on Nu Instruments MC-ICP Mass Spectrometers

    NASA Astrophysics Data System (ADS)

    Zhao, Ye; Hsieh, Yu-Te; Belshaw, Nick

    2015-04-01

    Silicon (Si) stable isotopes have been used in a broad range of geochemical and cosmochemical applications. A precise and accurate determination of Si isotopes is desirable to distinguish their small natural variations (< 0.2‰) in many of these studies. In the past decade, the advent of the MC-ICP-MS has spurred a remarkable improvement in the precision and accuracy of Si isotopic analysis. The instrumental mass fractionation correction is one crucial aspect of the analysis of Si isotopes. Two options are currently available: the sample-standard bracketing approach and the Mg doping approach. However, there has been a debate over the validity of the Mg doping approach. Some studies (Cardinal et al., 2003; Engström et al., 2006) favoured it compared to the sample-standard bracketing approach, whereas some other studies (e.g. De La Rocha, 2002) considered it unsuitable. This study investigates the Mg doping approach on both the Nu Plasma II and the Nu Plasma 1700. Experiments were performed in both the wet plasma and the dry plasma modes, using a number of different combinations of cones. A range of different Mg to Si ratios as well as different matrices have been used in the experiments. A sample-standard bracketing approach has also been adopted for the Si mass fractionation correction to compare with the Mg doping approach. Through assessing the mass fractionation behaviours of both Si and Mg under different instrument settings, this study aims to identity the factors which may affect the Mg doping approach and answer some key questions to the debate.

  9. Trends in arsenic levels in PM10 and PM 2.5 aerosol fractions in an industrialized area.

    PubMed

    García-Aleix, J R; Delgado-Saborit, J M; Verdú-Martín, G; Amigó-Descarrega, J M; Esteve-Cano, V

    2014-01-01

    Arsenic is a toxic element that affects human health and is widely distributed in the environment. In the area of study, the main Spanish and second largest European industrial ceramic cluster, the main source of arsenic aerosol is related to the impurities in some boracic minerals used in the ceramic process. Epidemiological studies on cancer occurrence in Spain points out the study region as one with the greater risk of cancer. Concentrations of particulate matter and arsenic content in PM10 and PM2.5 were measured and characterized by ICP-MS in the area of study during the years 2005-2010. Concentrations of PM10 and its arsenic content range from 27 to 46 μg/m(3) and from 0.7 to 6 ng/m(3) in the industrial area, respectively, and from 25 to 40 μg/m(3) and from 0.7 to 2.8 ng/m(3) in the urban area, respectively. Concentrations of PM2.5 and its arsenic content range from 12 to 14 μg/m(3) and from 0.5 to 1.4 ng/m(3) in the urban background area, respectively. Most of the arsenic content is present in the fine fraction, with ratios of PM2.5/PM10 in the range of 0.65-0.87. PM10, PM2.5, and its arsenic content show a sharp decrease in recent years associated with the economic downturn, which severely hit the production of ceramic materials in the area under study. The sharp production decrease due to the economic crisis combined with several technological improvements in recent years such as substitution of boron, which contains As impurities as raw material, have reduced the concentrations of PM10, PM2.5, and As in air to an extent that currently meets the existing European regulations.

  10. The binary fraction and mass segregation in Alpha Persei open cluster

    NASA Astrophysics Data System (ADS)

    Sheikhi, Najmeh; Hasheminia, Maryam; Khalaj, Pouria; Haghi, Hosein; Zonoozi, Akram Hasani; Baumgardt, Holger

    2016-03-01

    We have obtained membership probabilities of stars within a field of ˜ 3° from the centre of the open cluster Alpha Persei using proper motions and photometry from the PPMXL and Wide-field Infrared Survey Explorer catalogues. We have identified 810 possible stellar members of Alpha Persei. We derived the global and radial present-day mass function (MF) of the cluster and found that they are well matched by two-stage power-law relations with different slopes at different radii. The global MF of Alpha Persei shows a turnover at m = 0.62 M⊙ with low- and high-mass slopes of αlow = 0.50 ± 0.09 (0.1 < m/ M⊙ < 0.62) and αhigh = 2.32 ± 0.14 (0.62 ≤ m/ M⊙ < 4.68), respectively. The high-mass slope of the cluster increases from 2.01 inside 1.10° to 2.63 outside 2.2°, whereas the mean stellar mass decreases from 0.95 to 0.57 M⊙ in the same regions, signifying clear evidence of mass segregation in the cluster. From an examination of the high-quality colour-magnitude data of the cluster and performing a series of Monte Carlo simulations, we obtained a binary fraction of fbin = 34 ± 12 per cent for stars with 0.70 < m/ M⊙ < 4.68. This is significantly larger than the observed binary fraction, indicating that this open cluster contains a large population of unresolved binaries. Finally, we corrected the MF slopes for the effect of unresolved binaries and found low- and high-mass slopes of αlow = 0.89 ± 0.11 and αhigh = 2.37 ± 0.09 and a total cluster mass of 352 M⊙ for Alpha Persei.

  11. DDA Computations of Porous Aggregates with Forsterite Crystals: Effects of Crystal Shape and Crystal Mass Fraction

    NASA Astrophysics Data System (ADS)

    Wooden, Diane H.; Lindsay, Sean S.; Harker, David; Woodward, Charles; Kelley, Michael S. P.; Kolokolova, Ludmilla

    2015-08-01

    Porous aggregate grains are commonly found in cometary dust samples and are needed to model cometary IR spectral energy distributions (SEDs). Models for thermal emissions from comets require two forms of silicates: amorphous and crystalline. The dominant crystal resonances observed in comet SEDs are from Forsterite (Mg2SiO4). The mass fractions that are crystalline span a large range from 0.0 ≤ fcrystal ≤ 0.74. Radial transport models that predict the enrichment of the outer disk (>25 AU at 1E6 yr) by inner disk materials (crystals) are challenged to yield the highend-range of cometary crystal mass fractions. However, in current thermal models, Forsterite crystals are not incorporated into larger aggregate grains but instead only are considered as discrete crystals. A complicating factor is that Forsterite crystals with rectangular shapes better fit the observed spectral resonances in wavelength (11.0-11.15 μm, 16, 19, 23.5, 27, and 33 μm), feature asymmetry and relative height (Lindley et al. 2013) than spherically or elliptically shaped crystals. We present DDA-DDSCAT computations of IR absorptivities (Qabs) of 3 μm-radii porous aggregates with 0.13 ≤ fcrystal ≤ 0.35 and with polyhedral-shaped Forsterite crystals. We can produce crystal resonances with similar appearance to the observed resonances of comet Hale-Bopp. Also, a lower mass fraction of crystals in aggregates can produce the same spectral contrast as a higher mass fraction of discrete crystals; the 11µm and 23 µm crystalline resonances appear amplified when crystals are incorporated into aggregates composed otherwise of spherically shaped amorphous Fe-Mg olivines and pyroxenes. We show that the optical properties of a porous aggregate is not linear combination of its monomers, so aggregates need to be computed. We discuss the consequence of lowering comet crystal mass fractions by modeling IR SEDs with aggregates with crystals, and the implications for radial transport models of our

  12. The MODIS Aerosol Algorithm, Products and Validation

    NASA Technical Reports Server (NTRS)

    Remer, L. A.; Kaufman, Y. J.; Tanre, D.; Mattoo, S.; Chu, D. A.; Martins, J. V.; Li, R.-R.; Ichoku, C.; Levy, R. C.; Kleidman, R. G.

    2003-01-01

    The MODerate resolution Imaging Spectroradiometer (MODIS) aboard both NASA's Terra and Aqua satellites is making near global daily observations of the earth in a wide spectral range. These measurements are used to derive spectral aerosol optical thickness and aerosol size parameters over both land and ocean. The aerosol products available over land include aerosol optical thickness at three visible wavelengths, a measure of the fraction of aerosol optical thickness attributed to the fine mode and several derived parameters including reflected spectral solar flux at top of atmosphere. Over ocean, the aerosol optical thickness is provided in seven wavelengths from 0.47 microns to 2.13 microns. In addition, quantitative aerosol size information includes effective radius of the aerosol and quantitative fraction of optical thickness attributed to the fine mode. Spectral aerosol flux, mass concentration and number of cloud condensation nuclei round out the list of available aerosol products over the ocean. The spectral optical thickness and effective radius of the aerosol over the ocean are validated by comparison with two years of AERONET data gleaned from 133 AERONET stations. 8000 MODIS aerosol retrievals colocated with AERONET measurements confirm that one-standard deviation of MODIS optical thickness retrievals fall within the predicted uncertainty of delta tauapproximately equal to plus or minus 0.03 plus or minus 0.05 tau over ocean and delta tay equal to plus or minus 0.05 plus or minus 0.15 tau over land. 271 MODIS aerosol retrievals co-located with AERONET inversions at island and coastal sites suggest that one-standard deviation of MODIS effective radius retrievals falls within delta r_eff approximately equal to 0.11 microns. The accuracy of the MODIS retrievals suggests that the product can be used to help narrow the uncertainties associated with aerosol radiative forcing of global climate.

  13. Aerosol and trace gas vehicle emission factors measured in a tunnel using an Aerosol Mass Spectrometer and other on-line instrumentation

    NASA Astrophysics Data System (ADS)

    Chirico, Roberto; Prevot, Andre S. H.; DeCarlo, Peter F.; Heringa, Maarten F.; Richter, Rene; Weingartner, Ernest; Baltensperger, Urs

    2011-04-01

    In this study we present measurements of gas and aerosol phase composition for a mixed vehicle fleet in the Gubrist tunnel (Switzerland) in June 2008. PM 1 composition measurements were made with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (AMS) and a Multi Angle Absorption Photometer (MAAP). Gas-phase measurements of CO, CO 2, NO x and total hydrocarbons (THC) were performed with standard instrumentation. Weekdays had a characteristic diurnal pattern with 2 peaks in concentrations for all traffic related species corresponding to high vehicle density (˜300 ± 30 vehicles per 5 min) in the morning rush hour between 06:00 and 09:00 and in the afternoon rush hours from approximately 15:30 to 18:30. The emission factors (EF) of OA were heavily influenced by the OA mass loading. To exclude this partitioning effect, only organic aerosol mass concentrations from 60 μg m -3 to 90 μg m -3 were considered and for these conditions the EF(OA) value for HDV was 33.7 ± 2.3 mg km -1 for a temperature inside the tunnel of 20-25 °C. This value is not directly applicable to ambient conditions because it is derived from OA mass concentrations that are roughly a factor of 10 higher than typical ambient concentrations. An even higher EF(OA) HDV value of 47.4 ± 1.6 mg km -1 was obtained when the linear fit was applied to all data points including OA concentrations up to 120 μg m -3. Similar to the increasing EF, the OA/BC ratio in the tunnel was also affected by the organic loading and it increased by a factor of ˜3 over the OA range 10-120 μg m -3. This means that also the OA emission factors at ambient concentrations of around 5-10 μg m -3 would be 2-3 times lower than the emission factor given above. For OA concentrations lower than 40 μg m -3 the OA/BC mass ratio was below 1, while at an OA concentration of 100-120 μg m -3 the OA/BC ratio was ˜1.5. The AMS mass spectra (MS) acquired in the tunnel were highly correlated with the primary organic aerosol

  14. Influence of mass-transfer limitations on carbon isotope fractionation during microbial dechlorination of trichloroethene.

    PubMed

    Aeppli, Christoph; Berg, Michael; Cirpka, Olaf A; Holliger, Christof; Schwarzenbach, René P; Hofstetter, Thomas B

    2009-12-01

    Mass transfer of organic contaminants from nonaqueous phase liquids to the aqueous phase can significantly modulate the observable carbon isotope fractionation behavior associated with contaminant transformation. We evaluated the effects of kinetic interphase mass transfer between tetradecane and water on the observable (13)C enrichment factor, epsilon(obs), pertinent to the reductive dechlorination of trichloroethene (TCE) by Sulfurospirillum sp. in laboratory batch model systems containing organic, aqueous and gaseous phases. We propose a conceptual model, which includes the kinetics of tetradecane-water and gas-water mass transfer, microbial growth, and isotope-sensitive parameters describing dehalorespiration, for quantifying variable (13)C enrichment factors. While the C isotope fractionation of TCE reduction to cis-dichloroethene (cDCE) in the absence of phase-transfer effects can be characterized by a constant epsilon-value of -18.8 +/- 0.6 per thousand, mass-transfer limitations impede describing this process with a constant enrichment factor typically used in Rayleigh equations. Owing to the masking of kinetic isotope effects by the transfer of TCE from tetradecane to the aqueous phase, (obs)-values gradually changed from -18.4 per thousand to -5.9 per thousand. Such variations may complicate the interpretation of compound-specific isotope analysis in the assessment of chloroethene biodegradation in field applications.

  15. Aerosol volatility in a boreal forest environment

    NASA Astrophysics Data System (ADS)

    Häkkinen, S. A. K.; ńijälä, M.; Lehtipalo, K.; Junninen, H.; Virkkula, A.; Worsnop, D. R.; Kulmala, M.; Petäjä, T.; Riipinen, I.

    2012-04-01

    Climate and health effects of atmospheric aerosols are determined by their properties such as their chemical composition. Aerosol chemical composition can be studied indirectly by measuring volatility of aerosol particles. The volatility of submicron aerosol particles (20-500 nm) was studied in a boreal forest site at SMEAR II (Station for Measuring Ecosystem-Atmosphere Relations II) station (Vesala et al., 1998) in Hyytiälä, Finland, during 01/2008-05/2010. The instrument used for the measurements was VDMPS (Volatility Differential Mobility Particle Sizer), which consists of two separate instruments: DMPS (Differential Mobility Particle Sizer, Aalto et al., 2001) and TD (Thermodenuder, Wehner et al., 2002). Aerosol evaporation was examined by heating the aerosol and comparing the total aerosol mass before and after heating. In the VDMPS system ambient aerosol sample was heated up to temperatures ranging from 80 °C to 280 °C. The higher the heating temperature was the more aerosol material was evaporated. There was a non-volatile residual present in aerosol particles when heated up to 280 °C. This residual explained (20±8)% of the total aerosol mass. Aerosol non-volatile mass fraction was highest during winter and smallest during summer months. The role of black carbon in the observed non-volatile residual was determined. Black carbon explained 40 to 90% of the non-volatile mass. Especially during colder seasons noticeable amount of non-volatile material, something else than black carbon, was observed. According to Kalberer et al. (2004) some atmospheric organic species can form polymers that have high evaporation temperatures. Also low-volatile organic salts may contribute to the non-volatile aerosol (Smith et al., 2010). Aerosol mass composition measured directly with AMS (Aerosol Mass Spectrometer, Jayne et al., 2000) was analyzed in order to examine the properties of the non-volatile material (other than black carbon). The AMS measurements were performed

  16. Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

    NASA Astrophysics Data System (ADS)

    Das, R.; Odom, A. L.

    2007-12-01

    Mercury is long known as a common environmental contaminant. In methylated form it is even more toxic and the methylation process is facilitated by microbial activities. Methyl mercury easily crosses cell membrane and accumulates in soft tissues of fishes and finally biomagnifies with increasing trophic levels. Natural variations in the isotopic composition of mercury have been reported and such variations have emphasized mass dependent fractionations, while theory and laboratory experiments indicate that mass-independent isotopic fractionation (MIF) effects are likely to be found as well. This study focuses on the MIF of mercury isotopes in the soft tissues of fishes. Samples include both fresh water and marine fish, from different continents and oceans. Approximately 1 gm of fish soft tissue was dissolved in 5 ml of conc. aqua regia for 24 hrs and filtered through a ¬¬¬100 μm filter paper and diluted with DI water. Hg is measured as a gaseous phase generated by reduction of the sample with SnCl2 in a continuous- flow cold-vapor generator connected to a Thermo-Finnigan Neptune MC-ICPMS. To minimize instrumental fractionation isotope ratios were measured by sample standard bracketing and reported as δ‰ relative to NIST SRM 3133 Hg standard where δAHg = [(A Hg/202Hg)sample/(A Hg/202Hg)NIST313] -1 ×1000‰. In this study we have measured the isotope ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg and 204Hg/202Hg. In all the fish samples δ198Hg, δ200Hg, δ202Hg, δ204Hg define a mass- dependent fractionation sequence, where as the δ199Hg and δ201Hg depart from the mass- dependent fractionation line and indicate an excess of the odd-N isotopes. The magnitude of the deviation (ΔAHg where A=199 or 201) as obtained by difference between the measured δ199Hg and δ201Hg of the samples and the value obtained by linear scaling defined by the even-N isotopes ranges from approximately 0.2 ‰ to 3‰. The ratios of Δ199Hg /Δ201Hg range from 0.8 to 1

  17. Measurement and analysis of aerosol and black carbon in the southwestern United States and Panama and their dependence on air mass origin

    NASA Astrophysics Data System (ADS)

    Junker, C.; Sheahan, J. N.; Jennings, S. G.; O'Brien, P.; Hinds, B. D.; Martinez-Twary, E.; Hansen, A. D. A.; White, C.; Garvey, D. M.; Pinnick, R. G.

    2004-07-01

    Total aerosol mass loading, aerosol absorption, and black carbon (BC) content were determined from aerosol collected on 598 quartz fiber filters at a remote, semiarid site near Orogrande, New Mexico from December 1989 to October 1995. Aerosol mass was determined by weighing filters before and after exposure, and aerosol absorption was determined by measuring the visible light transmitted through loaded filter samples and converting these measurements to aerosol absorption. BC content was determined by measuring visible light transmitted through filter samples before and after firing and converting the absorption to BC mass, assuming a BC absorption cross section of 19 m2/g in the fiber filter medium. Two analyses were then performed on each of the logged variables: an autoregressive integrating moving average (ARIMA) analysis and a decomposition analysis using an autoregressive model to accommodate first-order autocorrelation. The two analyses reveal that BC mass has no statistically significant seasonal dependence at the 5% level of significance but only random fluctuations varying around an average annual value that has a long-term decreasing trend (from 0.16 to 0.11 μg/m3 during 1990-1995). Aerosol absorption, which is dominated by BC, also displays random fluctuations about an average value, and decreases from 1.9 Mm-1 to 1.3 Mm-1 during the same period. Unlike BC, aerosol mass at the Orogrande site displays distinctly different character. The analyses reveal a pronounced seasonal dependence, but no long-term trend for aerosol mass. The seasonal indices resulting from the autoregression analysis have a minimum in January (-0.78) and maximum in June (+0.58). The geometric mean value over the 1990-1995 period for aerosol mass is 16.0 μg/m3. Since BC aerosol at the Orogrande site is a product of long-range atmospheric transport, a back trajectory analysis of air masses was conducted. Back trajectory analyses indicate that air masses traversing high population

  18. High-resolution mass spectrometry and molecular characterization of aqueous photochemistry products of common types of secondary organic aerosols.

    PubMed

    Romonosky, Dian E; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

    2015-03-19

    This work presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d-limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow-tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx-generated SOA had more unique visual appearance and indicated a lower extent of product overlap. Furthermore, the fraction of nitrogen-containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone-driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NOx photooxidation of 1,3,5-trimethylbenzene and guaiacol were more resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of

  19. High-resolution mass spectrometry and molecular characterization of aqueous photochemistry products of common types of secondary organic aerosols.

    PubMed

    Romonosky, Dian E; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

    2015-03-19

    This work presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d-limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow-tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx-generated SOA had more unique visual appearance and indicated a lower extent of product overlap. Furthermore, the fraction of nitrogen-containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone-driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NOx photooxidation of 1,3,5-trimethylbenzene and guaiacol were more resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of

  20. Mass dependent stable isotope fractionation of mercury during mer mediated microbial degradation of monomethylmercury

    NASA Astrophysics Data System (ADS)

    Kritee, K.; Barkay, Tamar; Blum, Joel D.

    2009-03-01

    Controlling bioaccumulation of toxic monomethylmercury (MMHg) in aquatic food chains requires differentiation between biotic and abiotic pathways that lead to its production and degradation. Recent mercury (Hg) stable isotope measurements of natural samples suggest that Hg isotope ratios can be a powerful proxy for tracing dominant Hg transforming pathways in aquatic ecosystems. Specifically, it has been shown that photo-degradation of MMHg causes both mass dependent (MDF) and mass independent fractionation (MIF) of Hg isotopes. Because the extent of MDF and MIF observed in natural samples (e.g., fish, soil and sediments) can potentially be used to determine the relative importance of pathways leading to MMHg accumulation, it is important to determine the potential role of microbial pathways in contributing to the fractionation, especially MIF, observed in these samples. This study reports the extent of fractionation of Hg stable isotopes during degradation of MMHg to volatile elemental Hg and methane via the microbial Hg resistance ( mer) pathway in Escherichia coli carrying a mercury resistance ( mer) genetic system on a multi-copy plasmid. During experimental microbial degradation of MMHg, MMHg remaining in reactors became progressively heavier (increasing δ202Hg) with time and underwent mass dependent Rayleigh fractionation with a fractionation factor α202/198 = 1.0004 ± 0.0002 (2SD). However, MIF was not observed in any of the microbial MMHg degradation experiments indicating that the isotopic signature left by mer mediated MMHg degradation is significantly different from fractionation observed during DOC mediated photo-degradation of MMHg. Additionally, a clear suppression of Hg isotope fractionation, both during reduction of Hg(II) and degradation of MMHg, was observed when the cell densities increased, possibly due to a reduction in substrate bioavailability. We propose a multi-step framework for understanding the extent of fractionation seen in our MMHg

  1. Elemental Composition Analysis to Investigate NOx Effects on Secondary Organic Aerosol from α-Pinene Using Ultrahigh Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Lim, H. J.; Park, J. H.; Babar, Z.

    2015-12-01

    Secondary organic aerosol (SOA) accounts for 20-70% of atmospheric fine aerosol. NOx plays crucial roles in SOA formation and consequently affects the composition and yield of SOA. SOA component speciation is incomplete due to its complex composition of polar oxygenated and multifunctional species. In this study, ultrahigh resolution mass spectrometry (UHR MS) was applied to improve the understanding of NOx effects on biogenic SOA formation by identifying the elemental composition of SOA. Additional research aim was to investigate oligomer components that are considered as a driving force for SOA formation and growth. In this study α-pinene SOA from photochemical reaction was examined. SOA formation was performed in the absence and presence of NOx at dry condition (<5% RH) of room temperature (~25oC) in ~8 m3 KNU smog chamber. SOA was collected on Teflon-coated glass fiber filter, which was extracted using acetonitrile and analyzed by ultrahigh resolution 15T FT-ICR MS. UHR MS data were interpreted in various ways including molecular formula, Kendrick diagram, van Krevelen diagram, and double bond equivalent values. Substantially large fractions of them are nitrogen containing species. Thousands of individual species of SOA were identified. For SOA in the absence of NOx. intensity normalized mean O/C, H/C, N/C, OM/OC ratios were 0.43, 1.52, 0.02, and 1.68, respectively. For SOA in the presence of NOx, those ratios were 0.52, 0.95, 0.08, and 1.48, respectively. 4 different oligomer formation mechanisms (addition, H abstraction, hydrolysis and de-hydrolysis reaction) were examined on the basis of SOA compositions. Detailed discussion will be presented on the molecular structure and building block of oligomers in SOA as well as the evolution of individual elemental composition by multi-generation reactions. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-01350000).

  2. Mass-dependent and mass-independent fractionation of mercury isotopes in precipitation from Guiyang, SW China

    NASA Astrophysics Data System (ADS)

    Wang, Zhuhong; Chen, Jiubin; Feng, Xinbin; Hintelmann, Holger; Yuan, Shengliu; Cai, Hongming; Huang, Qiang; Wang, Shuxiao; Wang, Fengyang

    2015-11-01

    The isotopic composition of mercury (Hg) is increasingly used to constrain the sources and pathways of this metal in the atmosphere. Though China has the highest Hg production, consumption and emission in the world, Hg isotope ratios are rarely reported for Chinese wet deposition. In this study, we examined, for the first time outside North America, both mass-dependent fractionation (MDF, expressed as δ202Hg) and mass-independent fractionation of odd (odd-MIF, Δ199Hg) and even (even-MIF, Δ200Hg) Hg isotopes in 15 precipitation samples collected from September 2012 to August 2013 in Guiyang (SW China). All samples displayed significant negative δ202Hg (-0.44 ∼ -4.27‰), positive Δ199Hg (+0.19 to +1.16‰) and slightly positive Δ200Hg (-0.01‰ to +0.20‰). Potential sources of Hg in precipitation were identified by coupling both MDF and MIF of Hg isotopes with a back-trajectory model. The results showed that local emission from coal-fired power plants and cement plants and western long-range transportation are two main contributing sources, while the contribution of Hg from south wind events would be very limited on an annual basis. The relatively lower Δ200Hg values in Guiyang precipitation may indicate a dilution effect by local sources and/or insignificant even-MIF in the tropopause contribution of this subtropical region. Our study demonstrates the usefulness of isotope fractionation, especially MIF for tracing sources and pathways of Hg in the atmosphere.

  3. Mercury (Hg) in meteorites: Variations in abundance, thermal release profile, mass-dependent and mass-independent isotopic fractionation

    NASA Astrophysics Data System (ADS)

    Meier, Matthias M. M.; Cloquet, Christophe; Marty, Bernard

    2016-06-01

    We have measured the concentration, isotopic composition and thermal release profiles of Mercury (Hg) in a suite of meteorites, including both chondrites and achondrites. We find large variations in Hg concentration between different meteorites (ca. 10 ppb to 14,000 ppb), with the highest concentration orders of magnitude above the expected bulk solar system silicates value. From the presence of several different Hg carrier phases in thermal release profiles (150-650 °C), we argue that these variations are unlikely to be mainly due to terrestrial contamination. The Hg abundance of meteorites shows no correlation with petrographic type, or mass-dependent fractionation of Hg isotopes. Most carbonaceous chondrites show mass-independent enrichments in the odd-numbered isotopes 199Hg and 201Hg. We show that the enrichments are not nucleosynthetic, as we do not find corresponding nucleosynthetic deficits of 196Hg. Instead, they can partially be explained by Hg evaporation and redeposition during heating of asteroids from primordial radionuclides and late-stage impact heating. Non-carbonaceous chondrites, most achondrites and the Earth do not show these enrichments in vapor-phase Hg. All meteorites studied here have however isotopically light Hg (δ202Hg = ∼-7 to -1) relative to the Earth's average crustal values, which could suggest that the Earth has lost a significant fraction of its primordial Hg. However, the late accretion of carbonaceous chondritic material on the order of ∼2%, which has been suggested to account for the water, carbon, nitrogen and noble gas inventories of the Earth, can also contribute most or all of the Earth's current Hg budget. In this case, the isotopically heavy Hg of the Earth's crust would have to be the result of isotopic fractionation between surface and deep-Earth reservoirs.

  4. THE GENESIS SOLAR WIND CONCENTRATOR TARGET: MASS FRACTIONATION CHARACTERISED BY NE ISOTOPES

    SciTech Connect

    WIENS, ROGER C.; OLINGER, C.; HEBER, V.S.; REISENFELD, D.B.; BURNETT, D.S.; ALLTON, J.H.; BAUR, H.; WIECHERT, U.; WIELER, R.

    2007-01-02

    The concentrator on Genesis provides samples of increased fluences of solar wind ions for precise determination of the oxygen isotopic composition of the solar wind. The concentration process caused mass fractionation as function of the radial target position. They measured the fractionation using Ne released by UV laser ablation along two arms of the gold cross from the concentrator target to compare measured Ne with modeled Ne. The latter is based on simulations using actual conditions of the solar wind during Genesis operation. Measured Ne abundances and isotopic composition of both arms agree within uncertainties indicating a radial symmetric concentration process. Ne data reveal a maximum concentration factor of {approx} 30% at the target center and a target-wide fractionation of Ne isotopes of 3.8%/amu with monotonously decreasing {sup 20}Ne/{sup 22}Ne ratios towards the center. The experimentally determined data, in particular the isotopic fractionation, differ from the modeled data. They discuss potential reasons and propose future attempts to overcome these disagreements.

  5. Distillation of fermented sugarcane juice: fractions characterized by electrospray ionization mass spectrometry and multivariate data treatment.

    PubMed

    Canuto, Marcus H; Rosa, Carlos A; de Moura, Fabiana; Augusti, Rodinei; Siebald, Helmuth G L

    2012-07-01

    Direct infusion electrospray ionization mass spectrometry in the negative ion mode (ESI(-)-MS) was employed to discriminate among fractions arising from the distillation of fermented sugarcane juice during the production of cachaça, a typical Brazilian alcoholic beverage. Aliquots were collected in the course of distillation and their ESI(-)-MS shown to be almost indistinguishable by a simple visual inspection. However, when the ESI(-)-MS data were treated by the principal component analysis (PCA) and hierarchical clustering analysis (HCA) statistical methods, four major groups were clearly determined, the so-called head (two distinct clusters), heart and tail fractions. Furthermore, the recognition of diagnostic ions (and their respective intensities) enabled a more confident establishment of the cutoff position (i.e. the initial and final points of each fraction). In conclusion, ESI-MS, in conjunction with PCA or HCA approaches, proved to be a quite efficient method that allowed for a prompt characterization of each fraction derived from the distillation of brewed sugarcane. The results described herein can, therefore, be useful not only to optimize the production of cachaça but also to improve the quality of the final product.

  6. Distillation of fermented sugarcane juice: fractions characterized by electrospray ionization mass spectrometry and multivariate data treatment.

    PubMed

    Canuto, Marcus H; Rosa, Carlos A; de Moura, Fabiana; Augusti, Rodinei; Siebald, Helmuth G L

    2012-07-01

    Direct infusion electrospray ionization mass spectrometry in the negative ion mode (ESI(-)-MS) was employed to discriminate among fractions arising from the distillation of fermented sugarcane juice during the production of cachaça, a typical Brazilian alcoholic beverage. Aliquots were collected in the course of distillation and their ESI(-)-MS shown to be almost indistinguishable by a simple visual inspection. However, when the ESI(-)-MS data were treated by the principal component analysis (PCA) and hierarchical clustering analysis (HCA) statistical methods, four major groups were clearly determined, the so-called head (two distinct clusters), heart and tail fractions. Furthermore, the recognition of diagnostic ions (and their respective intensities) enabled a more confident establishment of the cutoff position (i.e. the initial and final points of each fraction). In conclusion, ESI-MS, in conjunction with PCA or HCA approaches, proved to be a quite efficient method that allowed for a prompt characterization of each fraction derived from the distillation of brewed sugarcane. The results described herein can, therefore, be useful not only to optimize the production of cachaça but also to improve the quality of the final product. PMID:22791258

  7. Mass spectrometric analysis and aerodynamic properties of various types of combustion-related aerosol particles

    NASA Astrophysics Data System (ADS)

    Schneider, J.; Weimer, S.; Drewnick, F.; Borrmann, S.; Helas, G.; Gwaze, P.; Schmid, O.; Andreae, M. O.; Kirchner, U.

    2006-12-01

    Various types of combustion-related particles in the size range between 100 and 850 nm were analyzed with an aerosol mass spectrometer and a differential mobility analyzer. The measurements were performed with particles originating from biomass burning, diesel engine exhaust, laboratory combustion of diesel fuel and gasoline, as well as from spark soot generation. Physical and morphological parameters like fractal dimension, effective density, bulk density and dynamic shape factor were derived or at least approximated from the measurements of electrical mobility diameter and vacuum aerodynamic diameter. The relative intensities of the mass peaks in the mass spectra obtained from particles generated by a commercial diesel passenger car, by diesel combustion in a laboratory burner, and by evaporating and re-condensing lubrication oil were found to be very similar. The mass spectra from biomass burning particles show signatures identified as organic compounds like levoglucosan but also others which are yet unidentified. The aerodynamic behavior yielded a fractal dimension (Df) of 2.09 +/- 0.06 for biomass burning particles from the combustion of dry beech sticks, but showed values around three, and hence more compact particle morphologies, for particles from combustion of more natural oak. Scanning electron microscope images confirmed the finding that the beech combustion particles were fractal-like aggregates, while the oak combustion particles displayed a much more compact shape. For particles from laboratory combusted diesel fuel, a Df value of 2.35 was found, for spark soot particles, Df [approximate] 2.10. The aerodynamic properties of fractal-like particles from dry beech wood combustion indicate an aerodynamic shape factor [chi] that increases with electrical mobility diameter, and a bulk density of 1.92 g cm-3. An upper limit of [chi] [approximate] 1.2 was inferred for the shape factor of the more compact particles from oak combustion.

  8. Ion mobility-mass spectrometry with a radial opposed migration ion and aerosol classifier (ROMIAC).

    PubMed

    Mui, Wilton; Thomas, Daniel A; Downard, Andrew J; Beauchamp, Jesse L; Seinfeld, John H; Flagan, Richard C

    2013-07-01

    The first application of a novel differential mobility analyzer, the radial opposed migration ion and aerosol classifier (ROMIAC), is demonstrated. The ROMIAC uses antiparallel forces from an electric field and a cross-flow gas to both scan ion mobilities and continuously transmit target mobility ions with 100% duty cycle. In the ROMIAC, diffusive losses are minimized, and resolution of ions, with collisional cross-sections of 200-2000 Å(2), is achieved near the nondispersive resolution of ~20. Higher resolution is theoretically possible with greater cross-flow rates. The ROMIAC was coupled to a linear trap quadrupole mass spectrometer and used to classify electrosprayed C2-C12 tetra-alkyl ammonium ions, bradykinin, angiotensin I, angiotensin II, bovine ubiquitin, and two pairs of model peptide isomers. Instrument and mobility calibrations of the ROMIAC show that it exhibits linear responses to changes in electrode potential, making the ROMIAC suitable for mobility and cross-section measurements. The high resolution of the ROMIAC facilitates separation of isobaric isomeric peptides. Monitoring distinct dissociation pathways associated with peptide isomers fully resolves overlapping peaks in the ion mobility data. The ability of the ROMIAC to operate at atmospheric pressure and serve as a front-end analyzer to continuously transmit ions with a particular mobility facilitates extensive studies of target molecules using a variety of mass spectrometric methods. PMID:23730869

  9. Comparison of Flamelet Models with the Transported Mass Fraction Approach for Supersonic Combustion

    NASA Astrophysics Data System (ADS)

    Li, Wenhai; Alabi, Ken; Ladeinde, Foluso

    2015-11-01

    In this study, two fully compressible RANS, LES, and combined RANS/LES flow solvers - AEROFLO and VULCAN, both of which were originally developed by the United States Department of Defense but have since been significantly enhanced and commercialized by our organization, are used to investigate the accuracy of flamelet-based approach when employed to model supersonic combustion. The flamelet results from both codes are assessed relative to solutions obtained by solving the transport equations for the mass fractions - which is also supported by one of the codes, and making familiar assumptions about the closure of the reaction rate. The studies are carried out in the flamelet regime, and the numerical procedures are based on high-order schemes, which are also used to solve the level-set and mixture fraction transport equations used to study, respectively, premixed and non-premixed combustion. The effects of supersonic Mach numbers on the results are discussed.

  10. Method for characterization of low molecular weight organic acids in atmospheric aerosols using ion chromatography mass spectrometry.

    PubMed

    Brent, Lacey C; Reiner, Jessica L; Dickerson, Russell R; Sander, Lane C

    2014-08-01

    The structural composition of PM2.5 monitored in the atmosphere is usually divided by the analysis of organic carbon, black (also called elemental) carbon, and inorganic salts. The characterization of the chemical composition of aerosols represents a significant challenge to analysts, and studies are frequently limited to determination of aerosol bulk properties. To better understand the potential health effects and combined interactions of components in aerosols, a variety of measurement techniques for individual analytes in PM2.5 need to be implemented. The method developed here for the measurement of organic acids achieves class separation of aliphatic monoacids, aliphatic diacids, aromatic acids, and polyacids. The selective ion monitoring capability of a triple quadropole mass analyzer was frequently capable of overcoming instances of incomplete separations. Standard Reference Material (SRM) 1649b Urban Dust was characterized; 34 organic acids were qualitatively identified, and 6 organic acids were quantified.

  11. [Application of on-line single particle aerosol mass spectrometry (SPAMS) for studying major components in fine particulate matter].

    PubMed

    Fu, Huai-yu; Yan, Cai-qing; Zheng, Mei; Cai, Jing; Li, Xiao-ying; Zhang, Yan-jun; Zhou Zhen; Fu, Zhong; Li, Mei; Li, Lei; Zhang, Yuan-Hang

    2014-11-01

    Based on preliminary studies by aerosol time-of-flight mass spectrometer (ATOFMS) and single particle aerosol mass spectrometer (SPAMS), typical methods for identifying the number of particles (or particle count) for five major components including sulfate, nitrate, ammonium, organic carbon (OC), and elemental carbon (EC) in China and abroad were summarized. In this study, combined with the characteristics of single particle mass spectrum by SPAMS, an optimized method is proposed. With field measurement using SPAMS during January 2013 in Beijing, particle counts of sulfate, nitrate, ammonium, OC, and EC determined by different methods were compared. The comparison with results of off-line filter analyses for these five components proved that the method proposed in this study is comparable and optimized. We also suggest factors needed to be considered in future application of SPAMS and other areas that require in-depth research. PMID:25639078

  12. A correlation equation for the mass median aerodynamic diameter of the aerosol emitted by solution metered dose inhalers.

    PubMed

    Ivey, James W; Lewis, David; Church, Tanya; Finlay, Warren H; Vehring, Reinhard

    2014-04-25

    A correlation equation for the mass median aerodynamic diameter (MMAD) of the aerosol emitted by solution metered dose inhalers (MDIs) is presented. A content equivalent diameter is defined and used to describe aerosols generated by evaporating metered dose inhaler sprays. A large set of cascade impaction data is analyzed, and the MMAD and geometric standard deviation is calculated for each datum. Using dimensional analysis, the mass median content equivalent diameter is correlated with formulation variables. Based on this correlation in combination with mass balance considerations and the definition of the aerodynamic diameter, an equation for prediction of the MMAD of an inhaler given the pressure of the propellant in the metering chamber of the MDI valve and the surface tension of the propellant is derived. The accuracy of the correlation equation is verified by comparison with literature results. The equation is applicable to both HFA (hydrofluoroalkane) propellants 134a and 227ea, with varying levels of co-solvent ethanol.

  13. [Application of on-line single particle aerosol mass spectrometry (SPAMS) for studying major components in fine particulate matter].

    PubMed

    Fu, Huai-yu; Yan, Cai-qing; Zheng, Mei; Cai, Jing; Li, Xiao-ying; Zhang, Yan-jun; Zhou Zhen; Fu, Zhong; Li, Mei; Li, Lei; Zhang, Yuan-Hang

    2014-11-01

    Based on preliminary studies by aerosol time-of-flight mass spectrometer (ATOFMS) and single particle aerosol mass spectrometer (SPAMS), typical methods for identifying the number of particles (or particle count) for five major components including sulfate, nitrate, ammonium, organic carbon (OC), and elemental carbon (EC) in China and abroad were summarized. In this study, combined with the characteristics of single particle mass spectrum by SPAMS, an optimized method is proposed. With field measurement using SPAMS during January 2013 in Beijing, particle counts of sulfate, nitrate, ammonium, OC, and EC determined by different methods were compared. The comparison with results of off-line filter analyses for these five components proved that the method proposed in this study is comparable and optimized. We also suggest factors needed to be considered in future application of SPAMS and other areas that require in-depth research.

  14. [Aging and mixing state of particulate matter during aerosol pollution episode in autumn Shanghai using a single particle aerosol mass spectrometer (SPAMS)].

    PubMed

    Mu, Ying-Ying; Lou, Sheng-Rong; Chen, Chang-Hong; Zhou, Min; Wang, Hong-Li; Zhou, Zhen; Qiao, Li-Ping; Huang, Cheng; Li, Mei; Li, Li; Wang, Qian; Huang, Hai-Ying; Zou, Lan-Jun

    2013-06-01

    A single particle aerosol mass spectrometer (SPAMS) was applied to characterize the size distribution (200 nm-2.0 microm) and chemical compositions of ambient particles during a polluted event from 11th to 18th, November 2011. OCEC, METAL, EC, SECONDARY and K-Na types of particulates were the dominant groups observed in